Hydroprocessing catalysts and methods for making thereof

ABSTRACT

An improved hydroprocessing slurry catalyst is provided for the upgrade of heavy oil feedstock. The catalyst comprises dispersed particles in a hydrocarbon medium with the dispersed particles have an average particle size ranging from 1 to 300 μm. The catalyst has a total pore volume of at least 0.5 cc/g and a polymodal pore distribution with at least 80% of pore sizes in the range of 5 to 2,000 Angstroms in diameter. The catalyst is prepared from sulfiding and dispersing a metal precursor solution in a hydrocarbon diluent, the metal precursor comprising at least a Primary metal precursor and optionally a Promoter metal precursor, the metal precursor solution having a pH of at least 4 and a concentration of less than 10 wt. % of Primary metal in solution.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit under 35 USC 119 of U.S. ProvisionalPatent Application No. 61/428,599 with a filing date of Dec. 30, 2010.This application claims priority to and benefits from the foregoing, thedisclosure of which is incorporated herein by reference.

TECHNICAL FIELD

The invention relates generally to catalysts for use in the conversionof heavy oils and residua and methods for making thereof.

BACKGROUND

The petroleum industry is increasingly turning to heavy crudes, resids,coals and tar sands as sources for feedstocks. Feedstocks derived fromthese heavy materials contain more sulfur and nitrogen than feedstocksderived from more conventional crude oils, requiring a considerableamount of upgrading in order to obtain usable products therefrom. Theupgrading or refining is accomplished by hydroprocessing processes,i.e., treating with hydrogen of various hydrocarbon fractions, or wholeheavy feeds, or feedstocks, in the presence of hydrotreating catalyststo effect conversion of at least a portion of the feeds, or feedstocksto lower molecular weight hydrocarbons, or to effect the removal ofunwanted components, or compounds, or their conversion to innocuous orless undesirable compounds.

Catalysts commonly used for these hydroprocessing reactions includematerials such as cobalt molybdate on alumina, nickel on alumina, cobaltmolybdate promoted with nickel, nickel tungstate, etc. U.S. Pat. Nos.4,824,821 and 5,484,755 and US Patent Publication No. 2006/0054535disclose hydroprocessing catalysts in the form of high activity slurry.The catalyst is produced from Group VIB metal compounds by sulfiding anaqueous mixture of the metal compounds with hydrogen sulfide (H₂S) gasat a pressure of up to 5,000 psi (340 atm). U.S. Pat. Nos. 7,754,645 and7,410,928 discloses a hydroprocessing catalyst and methods for makingthe catalysts, by reacting at least a Group VIB metal compound with aPromoter metal compound, sulfiding the intermediate mixture with asulfiding agent, then mixing the sulfided catalyst precursor with ahydrocarbon diluent to make a bulk slurry type catalyst.

There is still a need for improved catalysts with optimum morphology,structure and improved catalytic activity. There is also a need forimproved processes to prepare catalysts for use in the conversion ofheavy oils and residua.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to an improved process forpreparing a slurry catalyst composition for use in the upgrade of heavyoil feedstock. The process comprises: providing at least an inorganicmetal precursor solution comprising at least one of a Group VIB metalprecursor and a Group VIII metal precursor; mixing at least a polaraprotic solvent with the inorganic metal precursor solution to form anoil-dispersible inorganic metal precursor, at a weight ratio of solventto inorganic metal precursor solution of 1:1 to 100:1; and providing atleast a sulfiding agent to sulfide the oil-dispersible inorganic metalprecursor forming the slurry catalyst.

In one aspect, the invention relates to a process for preparing a slurrycatalyst composition for use in the upgrade of heavy oil feedstock. Theprocess comprises: providing a slurry catalyst prepared from at least aGroup VIB metal precursor compound and optionally at least a Promotermetal precursor compound selected from Group VIII, Group IIB, Group IIA,Group IVA metals and combinations thereof, wherein the slurry catalystcomprises a plurality of dispersed particles in a hydrocarbon mediumhaving an particle size ranging from 1 to 300 μm; providing a hydrogenfeed; treating the slurry catalyst by mixing with the hydrogen feed at apressure from 1435 psig (10 MPa) to 3610 psig (25 MPa) and a temperaturefrom 200° F. to 800° F. at a rate of from 500 to 15,000 scf hydrogen perbbl of slurry catalyst for a minute to 20 hours, wherein the slurrycatalyst is saturated with hydrogen providing an increase of k-values interms of HDS, HDN, and HDMCR of at least 15% compared to a slurrycatalyst that is not treated with hydrogen.

In one aspect, the invention relates to an improved process forpreparing a slurry catalyst with the use of rework materials. Theprocess comprises: providing at least a metal precursor comprising atleast a Group VIB metal, the metal precursor is a rework materialobtained from a process of making hydroprocessing catalysts, wherein therework material has an average particle size of less than 300 μm; mixingthe rework material with at least a diluent forming a slurried metalprecursor; and providing at least a sulfiding agent to sulfide theslurried metal precursor forming the slurry catalyst. In one embodiment,the sulfidation is in-situ with the heavy oil feedstock providing thesulfiding agent for the sulfidation.

In one aspect, the invention relates to a process for preparing a slurrycatalyst composition for use in the upgrade of heavy oil feedstock,using a pressure leach solution obtained from a metal recovery processas one of the metal precursor feed. The process comprises: providing atleast a metal precursor solution comprising at least a Primary metalprecursor in an aqueous solution, wherein the metal precursor solutionis a pressure leach solution obtained from a metal recovery process andwhere the at least a Primary metal precursor was previously leached intothe pressure leach solution in a leaching step; mixing the at least ametal precursor solution with at least a hydrocarbon diluent forming acatalyst precursor; and providing at least a sulfiding agent to sulfidethe catalyst precursor forming the slurry catalyst.

In another aspect, the invention relates to an improved process forforming a slurry catalyst. The process comprises: providing a metalprecursor solution comprising a mixture of at least two differentwater-soluble metal salts selected from Group VIB, Group VIII, GroupIVB, Group IIB metals and mixtures thereof; mixing the metal precursorsolution with a hydrocarbon diluent under high shear mixing to generatean emulsion with droplet sizes ranging from 0.1 to 300 μm; and sulfidingthe emulsion with at least a sulfiding agent to form the slurrycatalyst.

In one aspect, the invention relates to an improved slurry catalystcomposition. The slurry catalyst comprises a plurality of dispersedparticles in a hydrocarbon medium, wherein the dispersed particles havean average particle size ranging from 1 to 300 μm. The catalyst has apolymodal pore distribution with at least 80% of pore sizes in the rangeof 5 to 2,000 Angstroms in diameter. The catalyst is prepared fromsulfiding and dispersing a metal precursor solution in a hydrocarbondiluent, the metal precursor comprising at least a Primary metalprecursor, the metal precursor solution having a pH of at least 4 and aconcentration of less than 10 wt. % of Primary metal in solution.

In another aspect, the invention relates to an improved slurry catalyst.The catalyst a plurality of dispersed particles in a hydrocarbon medium,wherein the dispersed particles have an average particle size rangingfrom 1 to 300 μm, the slurry catalyst has a BET total surface area of atleast 100 m²/g, and the slurry catalyst is prepared from sulfiding anddispersing a metal precursor solution in a hydrocarbon diluent, themetal precursor comprising at least a Primary metal precursor andoptionally a Promoter metal precursor, the metal precursor solutionhaving a pH of at least 4 and a concentration of less than 10 wt. % ofPrimary metal in solution.

In one aspect, the invention relates to a process for preparing animproved slurry catalyst for the upgrade of heavy oil feedstock. Theprocess comprises: providing at least a metal precursor solutioncomprising at least a Primary metal precursor, the metal precursorsolution having a pH of at least 4 and a concentration of less than 10wt. % of the Primary metal in solution; sulfiding the at least a metalprecursor solution with a sulfiding agent, forming a sulfided catalystprecursor; and mixing the sulfided catalyst precursor with a hydrocarbondiluent to form the slurry catalyst wherein a slurry catalyst preparedtherefrom has an average particle size ranging from 1 to 300 μm, a BETtotal surface area of at least 100 m²/g, a polymodal pore distributionwith at least 80% of pore sizes in the range of 5 to 2,000 Angstroms indiameter, and a total pore volume of at least 0.5 cc/g.

In one aspect, the invention relates to an improved process forpreparing a slurry catalyst composition for use in the upgrade of heavyoil feedstock. The process comprises: providing at least a metalprecursor solution comprising at least two different metal cations inits molecular structure, with at least one of the metal cations is aGroup VIB metal cation; sulfiding the metal precursor with a sulfidingagent forming a catalyst precursor; and

mixing the catalyst precursor with a hydrocarbon diluent to form theslurry catalyst.

In one aspect, the invention relates to an improved process forpreparing a single-metal slurry catalyst. The process comprises:providing at least a Primary metal precursor, the Primary metal isselected from one of at least one of a non-noble Group VIII metal, aGroup VIB metal, a Group IVB metal, and a Group IIB metal; sulfiding thePrimary metal precursor with a sulfiding agent forming a catalystprecursor; and mixing the catalyst precursor with a hydrocarbon diluentto form a slurry catalyst having a particle size ranging from 1 to 300μm; and a general formula of(M^(t))_(a)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),wherein M is at least one of a non-noble Group VIII metal, a Group VIBmetal, a Group IVB metal, and a Group IIB metal; 0.5a<=d<=4a; 0<=e<=11a;0<=f<=18a; 0<=g<=2a; 0<=h<=3a; t, v, w, x, y, z, each representing totalcharge for each of: M, S, C, H, O, and N; and ta+vd+we+xf+yg+zh=0.

In another aspect, the invention relates to another improved process forpreparing a slurry catalyst. The process comprises: providing a metalprecursor solution comprising at least a water-soluble molybdenumcompound and a water-soluble metal zinc compound; mixing the metalprecursor solution with a hydrocarbon diluent under sufficiently highshear mixing to generate an emulsion with droplet sizes ranging from 0.1to 300 μm; sulfiding the emulsion precursor with at least a sulfidingagent to form a slurry catalyst having a particle size ranging from 1 to300 μm; and wherein the zinc compound is present in the slurry catalystin a sufficient amount for a zinc to molybdenum weight ratio rangingfrom 1:10 to 10:1.

In one aspect, the invention relates to yet another improved process forpreparing a slurry catalyst composition for use in the upgrade of heavyoil feedstock. The process comprises: providing at least a first metalprecursor comprising at least a metal salt of at least one of anon-noble Group VIII metal, a Group VIB metal, a Group IVB metal, and aGroup IIB metal; sulfiding the first metal precursor with a firstsulfiding agent to form a sulfided catalyst precursor; sulfiding thesulfided catalyst precursor with a second sulfiding agent at a molarratio of sulfur to metal in the sulfided catalyst precursor of at least1.5 to 1 for an enhanced sulfided catalyst precursor; and mixing theenhanced sulfided catalyst precursor with a hydrocarbon diluent forminga slurry catalyst having an average particle size of 1 to 300 μm.

In one aspect, the invention relates to an improved process forpreparing a slurry catalyst composition for use in the upgrade of heavyoil feedstock. The process to be improved comprises: providing a firstmetal precursor comprising at least a Group VIB metal and a promotermetal precursor comprising at least a promoter metal selected from GroupIVB metals, Group VIII metals, Group IIB metals and combinationsthereof, for a promoter metal to a Group VIB metal weight ratio rangingfrom 1:30 to 5:1; sulfiding the first metal precursor and the promotermetal precursor separately, concurrently, or together, forming apromoted sulfided catalyst precursor; and mixing the promoted sulfidedcatalyst precursor with a hydrocarbon diluent forming a slurry catalysthaving an average particle size of 1 to 300 μm. The improvementcomprises: apportioning at least one of the metal precursor into a firstportion and a second portion at a ratio of first portion to secondportion ranging from 1:10 to 10:1; employing the first portion in thesulfidation step to form the promoted sulfided catalyst precursor; andmixing the second portion with the promoted sulfided catalyst precursorbefore, during, or after the mixing step with a hydrocarbon diluent toform the slurry catalyst.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a block diagram illustrating one embodiment for preparing theslurry catalyst with at least two metal precursor feeds and with theco-sulfiding of the metal precursors in the continuous mode.

FIG. 2 is a block diagram illustrating another embodiment to prepare theslurry catalyst with a double salt metal precursor as a feed, within-situ sulfidation of the metal precursor.

FIG. 3 illustrates an embodiment to prepare the slurry catalyst, whereina pressure leach solution (PLS) or a leach slurry is used as a feed.

FIG. 4 is a block diagram illustrating another embodiment to prepare theslurry catalyst with the PLS as a feed.

FIG. 5 is a block diagram illustrating another embodiment to make aslurry catalyst with a hydrogen treatment step (prior to heavy oilupgrade).

FIG. 6 is a block diagram illustrating an embodiment to prepare a slurrycatalyst wherein metal precursors are mixed directly with a heavy oilfeedstock under high shear mixing.

FIG. 7 is a block diagram illustrating one embodiment to make slurrycatalyst with the use of a solvent and at least an inorganic metalprecursor for an oil dispersible metal precursor.

FIG. 8 is a block diagram illustrating a variation of the embodiment inFIG. 7 for making a promoted catalyst, with the use of an aproticsolvent for an oil dispersible metal precursor which is subsequentlysulfided.

FIG. 9 is a block diagram illustrating yet another variation of theembodiment in FIG. 8 with the use of an aprotic solvent.

FIG. 10 illustrates an embodiment to prepare a slurry catalyst with highshear mixing, forming an emulsion catalyst.

FIG. 11 illustrates a variation of the embodiment in FIG. 10 to preparea slurry catalyst with high shear mixing.

FIG. 12 illustrates another embodiment to prepare a slurry catalyst withhigh shear mixing, forming an emulsion, wherein the emulsion undergoesin-situ sulfidation.

FIG. 13 illustrates an embodiment to prepare a slurry catalyst usingrework material or ground residuum catalyst fines.

FIG. 14 illustrates an embodiment to prepare a promoted slurry catalystfrom an oil soluble organometallic compound as metal precursor feed,which subsequently thermally decomposes generating the sulfided slurrycatalyst.

FIG. 15 illustrates a variation of the embodiment in FIG. 14, whereinthe sulfiding is in-situ by mixing the oil soluble organometalliccompound with a heavy oil feed.

FIG. 16 illustrates an embodiment with a second sulfiding step for aslurry catalyst with enhanced amount of sulfur (double sulfiding).

FIG. 17 illustrates an embodiment to prepare a catalyst with Ti as apromoter.

FIG. 18 illustrates an embodiment to prepare a single metal catalyst,e.g., with the use of nickel as the single metal.

FIG. 19 illustrates an embodiment to prepare a Zn—Mo slurry catalyst.

FIG. 20 illustrates an embodiment for preparing a slurry catalyst with asplit feeding of at least a Promoter metal precursor feedstock.

FIG. 21 illustrates an embodiment for preparing a slurry catalyst fromground/rework catalyst.

DETAILED DESCRIPTION

The following terms will be used throughout the specification and willhave the following meanings unless otherwise indicated.

“Bulk catalyst” may be used interchangeably with “slurry catalyst” or“unsupported catalyst” or “self-supported catalyst,” meaning that thecatalyst composition is NOT of the conventional catalyst form with apreformed, shaped catalyst support which is then loaded with metals viaimpregnation or deposition catalyst. In one embodiment, the bulkcatalyst is formed through precipitation. In another embodiment, thebulk catalyst has a binder incorporated into the catalyst composition.In yet another embodiment, the bulk catalyst is formed from metalcompounds and without any binder. In one embodiment, the bulk catalystcomprises dispersed particles in a liquid mixture such as hydrocarbonoil (“slurry catalyst”).

“Heavy oil” feed or feedstock refers to heavy and ultra-heavy crudes,including but not limited to resids, coals, bitumen, tar sands, oilsobtained from the thermo-decomposition of waste products, polymers,biomasses, oils deriving from coke and oil shales, etc. Heavy oilfeedstock may be liquid, semi-solid, and/or solid. Examples of heavy oilfeedstock include but are not limited to Canada Tar sands, vacuum residfrom Brazilian Santos and Campos basins, Egyptian Gulf of Suez, Chad,Venezuelan Zulia, Malaysia, and Indonesia Sumatra. Other examples ofheavy oil feedstock include residuum left over from refinery processes,including “bottom of the barrel” and “residuum” (or “resid”),atmospheric tower bottoms, which have a boiling point of at least 650°F. (343° C.), or vacuum tower bottoms, which have a boiling point of atleast 975° F. (524° C.), or “resid pitch” and “vacuum residue” whichhave a boiling point of 975° F. (524° C.) or greater.

Properties of heavy oil feedstock may include, but are not limited to:TAN of at least 0.1, at least 0.3, or at least 1; viscosity of at least10 cSt; API gravity at most 15 in one embodiment, and at most 10 inanother embodiment. In one embodiment, a gram of heavy oil feedstockcontains at least 0.0001 grams of Ni/V/Fe; at least 0.005 grams ofheteroatoms; at least 0.01 grams of residue; at least 0.04 grams C5asphaltenes; at least 0.002 grams of micro residue (MCR); per gram ofcrude; at least 0.00001 grams of alkali metal salts of one or moreorganic acids; and at least 0.005 grams of sulfur. In one embodiment,the heavy oil feedstock has a sulfur content of at least 5 wt. % and anAPI gravity ranging from −5 to +5. A heavy oil feed such as Athabascabitumen (Canada) typically has at least 50% by volume vacuum reside. ABoscan (Venezuela) heavy oil feed may contain at least 64% by volumevacuum residue. A Borealis Canadian bitumen may contain about 5% sulfur,19% of asphaltenes and insoluble THF₁ (tetrahydrofuran) of less than 1kg/ton.

“Treatment,” “treated,” “upgrade,” “upgrading” and “upgraded,” when usedin conjunction with a heavy oil feedstock, describes a heavy oilfeedstock that is being or has been subjected to hydroprocessing, or aresulting material or crude product, having a reduction in the molecularweight of the heavy oil feedstock, a reduction in the boiling pointrange of the heavy oil feedstock, a reduction in the concentration ofasphaltenes, a reduction in the concentration of hydrocarbon freeradicals, and/or a reduction in the quantity of impurities, such assulfur, nitrogen, oxygen, halides, and metals.

The upgrade or treatment of heavy oil feeds is generally referred hereinas “hydroprocessing” (hydrocracking, or hydroconversion).Hydroprocessing is meant as any process that is carried out in thepresence of hydrogen, including, but not limited to, hydroconversion,hydrocracking, hydrogenation, hydrotreating, hydrodesulfurization,hydrodenitrogenation, hydrodemetallation, hydrodearomatization,hydroisomerization, hydrodewaxing and hydrocracking including selectivehydrocracking. The products of hydroprocessing may show improvedviscosities, viscosity indices, saturates content, low temperatureproperties, volatilities and depolarization, etc.

Hydrogen refers to hydrogen, and/or a compound or compounds that when inthe presence of a heavy oil feed and a catalyst react to providehydrogen.

“Surfactant” can be used interchangeably with “surface active agent,”“stabilizer,” or “surface modifier,” referring generally to any materialthat operates to lower the surface tension of a liquid or to reduce theliquid droplet size, thus improving the wetting at the interface betweenthe dispersed catalyst particles and the hydrocarbon oil.

“Catalyst precursor” refers to a compound containing one or morecatalytically active metals, from which compound the slurry catalyst iseventually formed, and which compound may be catalytically active as ahydroprocessing catalyst. An example is a water-based catalyst prior tothe transformation step with a hydrocarbon diluent, another example is asulfided metal precursor.

“One or more of” or “at least one of” when used to preface severalelements or classes of elements such as X, Y and Z or X₁-X_(n), Y₁-Y_(n)and Z₁-Z_(n), is intended to refer to a single element selected from Xor Y or Z, a combination of elements selected from the same common class(such as X₁ and X₂), as well as a combination of elements selected fromdifferent classes (such as X₁, Y₂ and Z_(n)).

SCF/BBL (or scf/bbl) refers to a unit of standard cubic foot of gas (N₂,H₂, etc.) per barrel of hydrocarbon feed, or slurry catalyst, dependingon where the unit is used.

The Periodic Table referred to herein is the Table approved by IUPAC andthe U.S. National Bureau of Standards, an example is the Periodic Tableof the Elements by Los Alamos National Laboratory's Chemistry Divisionof October 2001.

“Metal” refers to reagents in their elemental, compound, or ionic form.“Metal precursor” refers to the metal compound feed to the process. Theterm “metal” or “metal precursor” in the singular form is not limited toa single metal or metal precursor, e.g., a Group VIB or a Promotermetal, but also includes the plural references for mixtures of metals.“In the solute state” means that the metal component is in a proticliquid form.

“Group VIB metal” refers to chromium, molybdenum, tungsten, andcombinations thereof in their elemental, compound, or ionic form.

“Group VIII metal” refers iron, cobalt, nickel, ruthenium, rhenium,palladium, osmium, iridium, platinum, and combinations thereof.

“Primary metal” refers to a metal in its elemental, compound, or ionicform selected from any of Group VIB (IUPAC nomenclature Group 6), GroupVIII metals (IUPAC nomenclature Group s 8-10), Group IIB metals, andcombinations thereof, in its sulfided form functions as a catalyst in ahydroprocessing process. The Primary metal is present in a catalyst in alarger amount than other metals.

“Promoter metal” refers to a metal in its elemental, compound, or ionicform selected from any of Group IVB (IUPAC nomenclature Group 4), GroupVIB, Group VIII, Group IIB metals (IUPAC nomenclature Group 12), andcombinations thereof, added to increase the catalytic activity of thePrimary metal. Promoter metal is present in a smaller amount than thePrimary metal, in a range from 1-50 wt. % (Promoter metal to Primarymetal) in one embodiment, and from 2-30 wt. % in a second embodiment.

“Free of Promoter metal” or “substantially free of Promoter metal” meansthat in making the catalyst, no Promoter metal in their elemental,compound, or ionic form, is added. Traces of Promoter metals can bepresent, in an amount of less than 1% of the Primary metal (wt. %).

1000° F.+ conversion rate refers to the conversion of a heavy oilfeedstock having a boiling point of greater than 1000° F.+ to less than1000° F. (538° C.) boiling point materials in a hydroconversion process,computed as: 100%* (wt. % boiling above 1000° F. materials in feed−wt. %boiling above 1000° F. materials in products)/wt. % boiling above 1000°F. materials in feed).

“Pressure leach solution” or PLS, also known as “pregnant leachsolution,” “pregnant leach liquor,” or “leach solution” refers to acomposition obtained from recovery of metals from metallurgical wastes,mineral ores and/or concentrates, spent batteries, or spent catalysts,wherein a leaching step under pressure and temperature is employed todissolve or cause the leaching of certain metal component(s) into theaqueous phase, giving a pressure leach solution.

“Pressure leach slurry,” also known as “leach slurry,” refers to aslurry resulting from the dissolution of metals such as Group VIBmetals, Promoter metals, and the like, from a spent catalyst. In oneembodiment wherein the leach slurry is from a metal recovery process,e.g., recovery of metals from spent slurry catalyst, the pressure leachslurry may contain coke in an amount of 1 to 20 wt. %.

“Dispersion” also known as “emulsion” refers to two immiscible fluids inwhich one fluid (e.g., catalyst precursor, metal precursor, etc.) issuspended or dispersed in the form of droplets in the second fluid phase(e.g., heavy oil feedstock or hydrocarbon diluent) as the continuousphase. In one embodiment, the droplets are in the range of 0.1 to 300μm. In another embodiment, from 1 to 10 μm. In a third embodiment, thedroplets are in the range of 0.5 to 50 μm in size. The droplets cansubsequently coalesce to be larger in size. Droplet size can be measuredby methods known in the art, including particle video microscope andfocused beam reflectance method, as disclosed in Ind. Eng. Chem. Res.2010, 49, 1412-1418, the disclosure of which is herein incorporated inits entirety by reference.

“Rework” “may be used interchangeably with “rework materials” or“catalyst fines,” referring to catalyst products, scrap pieces, fines,or rejected materials obtained from the process of making any of asupported catalyst, a self-supported catalyst, and a catalyst precursor,reduced in size to fines or powdered materials containing one or morecatalytic materials. The catalyst fines can be generated from a catalystproduct, or from the rejected materials/scrap pieces containingcatalytic materials generated in the process of making the catalystproduct. The catalyst fines can be sulfided or unsulfided. In oneembodiment, the rework is from making unsupported catalyst precursor,wherein the rework is generated from final products, catalyst fines,broken pieces, scrap pieces and the like, and before the catalystprecursor is sulfided. In another embodiment, the rework is generatedfrom of fines, final products, scrap pieces, etc., generated from theprocess of forming/shaping a catalyst precursor and before thesulfidation step. In another embodiment, the rework is in the form offines generated from grinding any of supported catalyst products,unsupported catalyst products, scrap pieces, fines, and combinationsthereof, generated in a process to make a supported catalyst or anunsupported catalyst.

Reaction rate constants (“k-values”) for reactions such as HDN, HDS, andHDMCR refer to the constant of proportionality which relates the rate ofconversion of a particular fraction (VGO, VR, etc.), or of particularclass of compounds in the feed (sulfur-containing or HDS, nitrogencontaining or HDN), to the appropriate functions of the process, such asthe concentration of the reactants, process pressure, flow rate, andother process-specific variables. As computed herein, the totalvolumetric flow rate to the system (LHSV) includes the fresh VR streamis corrected to account for the effect of gas hold-up.

Pore porosity and pore size distribution in one embodiment are measuredusing mercury intrusion porosimetry, designed as ASTM standard method D4284. Unless indicated otherwise, pore porosity is measured via thenitrogen adsorption method.

In one embodiment, the invention relates to methods for making slurrycatalysts having improved properties including but not limited to highsurface area and large pore volume. The invention also relates to amethod for the hydroconversion or upgrade of heavy oils, by sending theheavy oil feed to the upgrade process in the presence of the improvedslurry catalyst, operating under conditions to get at least 30% 1000°F.+ conversion in one embodiment, at least 50% 1000° F.+ in anotherembodiment.

Metal Precursor(s) Feed: In one embodiment, the catalyst is preparedfrom at least a Primary metal component (e.g., a Group VIB metalprecursor) and at least one Promoter metal precursor (e.g., a Group VIIImetal precursor, a Group IIB metal precursor, or a Group VIII metalprecursor such as Ni and a Group IVA metal precursor such as Ti). Inanother embodiment, the catalyst is prepared from at least a Primarymetal precursor with no Promoter metal added. In yet another embodiment,the catalyst is prepared from at least a Group VIII metal such as anickel compound as the Primary metal component, with or without thesubsequent addition of other metals as Promoter metals. In yet anotherembodiment, the catalyst is prepared from a double salt precursorcontaining at least two different metal cations, e.g., prepared from atleast two different metal precursor feeds. Multiple Promoter metalprecursors can be used as the feedstock, e.g., different Group VIIImetal precursors are used such as Ni and Co. Multiple Primary metalprecursors can be used as co-catalyst, e.g., Mo and W.

In embodiments with the addition of at least a Promoter metal, theweight ratio of the Promoter metal component to the Primary metalcomponent is in the range of 1 to 90%. In a second embodiment, the ratioranges from 2 to 50%. In a third embodiment, from 5 to 30%. In a fourthembodiment, from 10 to 20%.

In one embodiment, at least one of the metal precursors may be oilsoluble, oil dispersible, water soluble and/or water dispersible. Themetal precursors can be provided as an elemental metal or as a metalcompound. The metal precursors can be added in the solid state. In oneembodiment, one of the metal precursors can be added in the solid state,while the second metal precursor can be added in the solute state. Themetal precursors can be the same or different, e.g., all organiccompounds, all inorganic compounds, or one organic and one inorganic.The metal precursors in one embodiment can be catalytically active,e.g., a reagent grade metal sulfide or a beneficiated ore.

In one embodiment, at least one of the metal precursors is an organiccompound selected from metal salts of organic acids, such as acyclic andalicyclic aliphatic, carboxylic acids containing two or more carbonatoms. Non-limiting examples include acetates, oxalates, citrates,naphthenate and octoates. In another embodiment, the metal precursorsare selected from salts of organic amines. In yet another embodiment,the metal precursors are selected from organometallic compounds, e.g.,chelates such as 1,3-diketones, ethylene diamine, ethylene diaminetetraacetic acid, phthalocyanines and mixtures thereof. In anotherembodiment, the organic metal precursors are selected from salts ofdithiolate, dithiocarbamate, and mixtures thereof. An example is a GroupVIII metal precursor such as a dithiocarbamate complex. Another exampleof a Group VIB metal precursor is a soluble molybdenum-containingorganophosphorodithioate such as molybdenum dialkyl dithiophosphate. Themetal precursors can also be sulfur-containing organic compounds, e.g.,a chelate compound with sulfur as a coordinating atom such as sulfhydrylS—H, or a molybdenum oxysulfide dithiocarbamate complex (Molyvan A).

In one embodiment, the Group VIB metal precursor (as a Primary metal ora Promoter metal) is selected from the group of alkali metal or ammoniummetallates of molybdenum in organic solvents such as a normal alkane,hydrocarbons, or petroleum products such as distillate fractions whereinthe molybdenum compound is allowed to subsequently decompose underpressure and temperature, prior to or concurrent with the addition ofthe Promoter metal precursor.

In one embodiment, the Group VIB metal precursor feed is a water-solublesalt, e.g., oxides and polyanions such as molybdates, tungstates,chromates, dichromates, etc. In one embodiment, the Group VIB metalprecursor is selected from the group of alkali metal heptamolybdates,alkali metal orthomolybdates, alkali metal isomolybdates,phosphomolybdic acid, and mixtures thereof. In another embodiment, it isselected from the group of molybdenum (di- and tri) oxide, molybdenumcarbide, molybdenum nitride, aluminum molybdate, molybdic acid (e.g.H₂MoO₄), or mixtures thereof. In yet another embodiment, the Group VIBmetal compound is an organometallic complex, e.g., oil soluble compoundor complex of transition metal and organic acid, selected fromnaphthenates, pentanedionates, octoates, acetates, and the like.Examples include molybdenum naphthenate and molybdenum hexacarbonyl.

In one embodiment, the at least one of Group VIII metal precursor (as aPromoter metal or as a Primary metal component) is selected frominorganic compounds, including but not limited to sulfates, nitrates,carbonates, sulfides, oxysulfides, oxides and hydrated oxides, ammoniumsalts and heteropoly acids thereof. In one embodiment, the Group VIIImetal precursor is a water-soluble compound such as acetate, carbonate,chloride, nitrate, acetylacetone, citrate, sulfate, and oxalate, e.g.,nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, etc.,and mixtures thereof. In another embodiment, the metal precursor is acompound which is at least partly in the solid state, e.g., awater-insoluble nickel compound such as nickel carbonate, nickelhydroxide, nickel phosphate, nickel phosphite, nickel formate, nickelsulfide, nickel molybdate, nickel tungstate, nickel oxide, nickel alloyssuch as nickel-molybdenum alloys, Raney nickel, or mixtures thereof.

In one embodiment, a Group IIB metal precursor such as zinc is employedas a Promoter metal (instead of a Group VIII metal precursor). Zinc is aless expensive material and more environmentally friendly than othermetal precursors such as nickel. Examples include but are not limitedGroup IIB inorganic compounds such as zinc sulfate, zinc nitrate, zinccarbonate, zinc sulfide, zinc oxysulfide, zinc oxide and zinc hydratedoxide, zinc ammonium salts and heteropoly acids thereof. Other examplesof zinc as a Promoter metal precursor include oil soluble organic acidsalts such as zinc acetate, zinc oxylate, zinc citrate, zinc napthanateand zinc octoates. In another embodiment, the Promoter metal precursoris selected from zinc salts of organic amines such as aliphatic amines,aromatic amines, quaternary ammonium compounds, and mixtures thereof. Inyet another embodiment, the zinc metal precursors are selected fromorganometallic compounds such as chelates including chelate compoundswith sulfur as a coordinating atom, e.g., thiols such asdialkyldithiophosphates, thio- or dithiocarbamates, phosphorothioates,thiocarbonates, trimercaptotriazine, thiophenates, mercaptans, thiolcarboxylic acids RC(O)SH, dithio acids RC(S)SH, and related compounds.

Organic Solvent Feed: In one embodiment with the use of organometalliccompounds as metal precursors, the solubility of the catalyst precursorin oil is increased, which may lead to higher dispersion and more activecatalyst particularly if the catalyst precursor is to be sulfideddirectly in a heavy oil feedstock. Organometallic compounds can beexpensive compared to inorganic compounds, but inorganic metalprecursors are not soluble in oil. In one embodiment, polar aproticsolvents are used in conjunction with inorganic metal precursors for thepreparation of the precursor feed. The organic solvent, e.g., anorganosulfur compound which is compatible with both the inorganic metalprecursor and the oil feedstock, acts as a solvent to dissolve theinorganic metal precursor. With the use of the organic solvent, theinorganic metal precursor becomes dispersible in the heavy oilfeedstock, thus alleviating the need for a transforming step. In oneembodiment with the use of an organic solvent to help disperse theinorganic metal precursor in the heavy oil feedstock, a separatesulfiding step can be eliminated as the metal precursor can be sulfidedwith sulfur sources inherently present in the heavy oil feedstock.

In one embodiment, the organic solvent is selected from the group ofpolar aprotic solvents such as N-Methylpyrrolidone (NMP),dimethylformamide (DMF), dimethylacetamide (DMAC),hexamethylphosphortriamide (HMPA), dimethyl sulfoxide (DMSO),tetrahydrofuran, propylene carbonate, dimethyl sulfite,N-nitrosodimethylamine, γ-butyrolactone, N:N dimethyl formamide,dimethyl carbonate, methyl formate, butyl formate and mixtures thereof.The organic solvent can be used as neat liquids, or in combination withother inexpensive solvents such as water or methanol. Examples ofinorganic metal precursors for use with the organic solvent include butare not limited to molybdenum oxide, sulfide, or oxysulfide of thegeneral formula MoO_(x)S_(y) wherein x≧0, y≧0. In one embodiment, theGroup VIB inorganic metal precursor is molybdenum trioxide. In anotherembodiment, the inorganic metal precursor is ammonium heptamolybdate.

In one embodiment, oil soluble metal precursors are formed by theinteraction of precursors such as ammonium paramolybdate with higheralcohols, glycols, and alkylsalicylic acids. In one example, ammoniumparamolybdate is added to concentrated ammonia, at least an oil solubledispersant, and aromatic solvent such as toluene or xylene. In anotherexample, an oil soluble metal precursor can be prepared from by reactinginorganic metal precursors with polyamides, succinimides and sulfonates.In another example, an oil-soluble sulfur containing metal precursor isprepared by treating with hydrogen sulfide a mixture of ammoniumparamolybdate and succinimide In another embodiment, the oil-solublemetal precursors prepared from inorganic salts are commerciallyavailable products including but not limited to OLOA 11007 and OLOA 378,available from Chevron Oronite and Molyvan™ A from RT VanderbiltCompany. In one embodiment, Molyvan™ A additive is used by itself forthe preparation of Mo-only catalyst. In another embodiment, Molyvan™ Aadditive is used in conjunction with nickel naphthenate for thepreparation of Ni-promoted slurry catalyst.

In one embodiment, the inorganic metal precursor is dissolved in theorganic solvent in a weight ratio of 1:4 to 4:1; a weight ratio of 1:3to 2:1 in a second embodiment; and a weight ratio of 1:5 to 1:1 in athird embodiment.

Pressure Leach Solution as a Metal Precursor Feed In yet embodiment, apressure leach solution (PLS) from a metal recovery process can be usedas the metal precursor feedstock or part of the metal precursorfeedstock. The metal recovery process can be part of a mining/oreoperation, an electroplating operation, or recovery of metals from spentcatalysts, and the like. A PLS composition may contain a single metalprecursor in aqueous solution, or a mixture of metal components such asGroup VIB metal and at least another metal precursor. An example of apressure leach solution (PLS) may contain any of ammonium heptamolybdate(AHM), nickel sulfate, nickel amine sulfate, ammonium metavanadate,ammonium sulfamate and the like. In one embodiment, a PLS streamcontaining 50 to 90 gpL (grams per liter) molybdenum, 3 to 10 gpLnickel, 0.1 to 1 gpL vanadium, 100 to 500 gpL ammonium sulfate, and 5 to30 gpL ammonium sulfamate can be used as the metal precursor feed. Inanother embodiment, the PLS stream contains 20 to 100 gpL (grams perliter) molybdenum, 5 to 20 gpL nickel, 0.10 to 1.0 gpL vanadium, 100 to500 gpL ammonium sulfate, and 5 to 20-gpL ammonium sulfamate.

In one embodiment and depending on the pH of the pressure leach solution(PLS), some of the metals in the PLS may precipitate wherein the PLS isin the form of a slurry, which can also be used directly as a feed tothe process. Details regarding a metal recovery process, and leachstream compositions, and pressure leach slurry compositions from therecovery of metals in spent catalysts can be found in U.S. Pat. Nos.7,837,960, 7,846,404 and 7,658,895, and U.S. patent application Ser. No.13/156,589, the relevant disclosures are included herein by reference.In one embodiment, the pressure leach solution in the form of a slurrycontains 1-20 wt. % coke and 0.2-4 wt % partially insoluble ammoniummetavanadate, which can be filtered out before the solution can be usedas metal precursor feedstock.

Double Salt as a Metal Precursor Feedstock: In one embodiment, insteadof or in addition to single metal precursor feeds, at least one of themetal precursors is a double salt precursor. A double salt metalprecursor is a metal precursor having at least two different metalcations in the molecular structure, with at least one of metal cationsbeing a Primary metal cation and at least one Promoter metal cation,e.g., ammonium nickel molybdate (formed from ammonium molybdate withnickel sulfate). It should be noted that the term “double” is notlimited to two metal cations. The double salt precursor can be formedfrom at least three different metal cations.

In one embodiment, one of the metal cations in the double salt precursoris a Group VIB cation such as molybdenum and the other metal cation is adifferent cation metal such as nickel or zinc. In another embodiment,the double salt precursor is characterized has having three differentmetal cations, with two of metal cations are different Group VIB metalcations such as molybdenum and tungsten, and the third cation is a GroupVIII metal cation such as nickel or zinc. In yet another embodiment, thedouble salt precursor comprises three different metal cations, with twoof metal cations are different Promoter metal cations such as nickel andtitanium, and the third cation is a Primary metal cation such asmolybdenum. The use of a double salt as a precursor reagent,particularly in crystal form or in concentrated form as a slurry, canreduce cost in terms of transport to the site to make the slurrycatalyst. Additionally, better catalyst performance is possible with thePromoter metal(s) being in the same molecular structure, in closeproximity with the Primary metal component when the double salt metalprecursor is sulfided, either in-situ or in a separate sulfidation step.

In one embodiment, the double salt precursor is a water-soluble salt,e.g., prepared from crystallizing an aqueous solution of a mixture of atleast a Group VIB metal salt and a Group VIII or Group IIB metal salt,e.g., ammonium molybdate and nickel sulfate, ammonium molybdate and zincsulfate, ammonium octamolybdate and a double salt of nickel ammoniumsulfate, potassium molybdate and iron sulfate, potassium chromiumsulfate and ammonium para-molybdate, etc. In one embodiment, the pH ofthe aqueous solution of the salt mixture is adjusted with the additionof an acid and/or a base to a pre-selected pH for the double salt tocrystallize out of solution. At the pre-select pH which does not favorthe solubility of the multi-metallic bimetallic compound, a double saltprecipitates out. The formation of the precipitate ensures that thedifferent metals constituting the catalyst precursor are well dispersedtogether in the solid phase.

In one embodiment, the double salt metal precursor is prepared from apressure leach solution or a leach slurry from a metal recovery process,optionally with the adjustment of the pH and/or the addition of a metalsalt in aqueous solution form to cause the precipitate of the doublesalt for use as a metal precursor feed.

In one embodiment, the double salt is an oil-soluble salt prepared bythe reaction of at least a Group VIII metal precursor or a Group IIBmetal precursor, and at least a Group VIB organometallic complex. Inanother embodiment, the double salt is prepared by the reaction of anoil soluble molybdenum salt and an oil soluble transition metal salt. Inone embodiment, the reaction to form the oil-soluble double saltprecursor is in the presence of a strong reducing agent such ashydrogen. In one embodiment, the Primary metal oil soluble compound isselected from naphthenates, pentanedionates, octoates, acetates, andmixtures thereof. Examples include but are not limited to molybdenumnaphthenate and molybdenum hexacarbonyl.

In one embodiment, the reaction to form the oil-soluble double salt iscarried out at a temperature of at least 100° C. for a sufficient lengthof time, e.g., between 2 hours and 48 hours. In another embodiment, thereaction to form the oil-soluble double agent is carried out in areducing environment and in the presence of an inert, water-immiscible,organic solvent. Examples of organic solvents include but are notlimited to aliphatic or aromatic hydrocarbons or chlorinatedhydrocarbons such as benzene, toluene, xylene, ethylbenzene, dipentene,turpentine, petroleum products such as gasoline, mineral spirits,kerosene, mineral oil, fuel oil, aromatic naphthas, and chlorinatedhydrocarbons as CCl₄, o-dichlorobenzene, monochlorotoluene, ethylenedichloride, perchloroethylene, and mixtures thereof.

In one embodiment, the reaction to form the double salt precursor iscarried out under conditions that exceed the boiling point of water suchthat water is removed as it is formed during the reaction. The water isallowed to escape from the reaction vessel as water vapor. In yetanother embodiment, chemical drying agents such as calcium chloride oran azeotropic agent can be employed to remove water from the reactionproduct to form the oil-soluble double salt, although this is usuallynot necessary. Any known solid separation techniques can also be usedsuch as filtering and the like.

In one embodiment, at least half of the Primary metal precursorfeedstock and/or Promoter metal precursor is in solution at aconcentration of less than 10 wt. % with the addition of appropriatediluent, e.g., water for a water-soluble metal precursor or ahydrocarbon diluent such as an olefinic diluent or a cycle oil for anoil-based metal precursor, forming a metal precursor solution,suspension, or emulsion. In selecting the appropriate diluent for themetal precursor feedstock, one or more criteria may be used, including,but not limited to: the flash point of the diluent, the inert nature ofthe diluent under certain conditions as related to the catalytic processin which the metal precursor is used, the ability of the diluent tocause the metal precursor to be fluid-like and moveable at theappropriate temperatures and pressures, and/or the ability of thediluent to present certain processing advantages in subsequentprocesses. For example, it may be advantageous to select a diluent thatdoes not react with the metal precursor at standard storage andtransportation temperatures, but provides for a stable solution of metalprecursor that may be stored or shipped over long distances to afacility that further prepares and/or uses the metal precursor/diluentscomposition to make the slurry catalyst.

In one embodiment, a sufficient amount of diluent is added to the metalprecursor feedstock for the solution to have a pH of at least 4. In asecond embodiment, the precursor feedstock has a pH of at least 5. In athird embodiment, the precursor feedstock has a pH of at least 6. Themetal precursor feedstock is in solution with a concentration of metalbetween 1-5 wt. % in one embodiment; between 0.1-10 wt. % in anotherembodiment; between 0.1 to 2 wt. % in a third embodiment. In oneembodiment, the metal concentration in at least one of the metalprecursor solution is between 5-8 wt. %. In another embodiment, at leastone of the metal precursor feedstock is a solution with a pH of at least4 and a metal concentration of 5 to 8 wt. %. In one embodiment, themetal precursor comprises at least a Primary metal in an aqueoussolution with a concentration of 0.25-10 wt. %. In another embodiment,the Promoter metal concentration is also in aqueous solution with aconcentration of less than 10 wt. % metal. In yet another embodiment, atleast one of the metal precursor feedstock is in solution at aconcentration between 0.1 and 8 wt. %.

Rework Materials as Metal Precursor Feedstock: In one embodiment, atleast a portion of the metal precursor feedstock is in a solid form,more specifically in the form of “rework.” Examples include reworkmaterials generated in the making of supported and unsupported (mixedGroup VIII and Group VIB metal) catalyst precursors used forhydroconversion processes known in the art. In one embodiment, therework materials are prepared from a supported catalyst, e.g., a metalprecursor or catalyst precursor such as a metal oxide or metalhydroxide, affixed onto a porous refractory base (“a carrier”)comprising one or more of alumina, silica, magnesia, titania, zeolite,silica-aluminate, carbon, phosphorous or various combinations of these.The alumina in the base can be in several forms including amorphous,alpha, gamma, theta, boehmite, pseudo-boehmite, gibbsite, diaspore,bayerite, nordstrandite and corundum. In one embodiment, the alumina isboehmite or pseudo-boehmite. In another embodiment, the rework materialsare prepared from an unsupported or bulk catalyst with or without theuse of a diluent or binder material (e.g., cellulose), such as catalystprecursor comprising a metal oxide or metal hydroxide. The metals thatare used in the supported catalyst going into rework materials includebase metals or compounds thereof, selected from Group VIB metals orGroup VIII metals of the Periodic Table, or combinations thereof.

Examples of supported and unsupported catalyst precursors and processfor making thereof are as disclosed in U.S. Pat. Nos. 2,238,851;4,113,661; 4,066,574; 4,341,625; 5,841,013; 6,156,695; 6,566,296;6,860,987; 7,544,285; 7,615,196; 6,635,599; 6,635,599; 6,652,738;7,229,548; 7,288,182; 6,162,350; 6,299,760; 6,620,313; 6,758,963;6,783,663; 7,232,515; 7,179,366; 6,274,530; 7,803,266; 7,185,870;7,449,103; 8,024,232; 7,618,530; 6,589,908; 6,667,271; 7,642,212;7,560,407, 6,030,915, 5,980,730, 5,968,348, 5,498,586; and US PatentPublication Nos. US2009/0112011A1, US2009/0112010A1, US2009/0111686A1,US2009/0111685A1, US2009/0111683A1, US2009/0111682A1, US2009/0107889A1,US2009/0107886A1, US2009/0107883A1, US2011/0226667, US2009/0310435,US2011/0306490A1, and US2007/090024, the relevant disclosures areincluded herein by reference.

In one embodiment, rework materials for use as metal precursor feedcomprise scrap/discarded/unused materials generated in any step of thepreparation of (unsulfided) catalyst/catalyst precursor. Rework can begenerated from any of the forming, drying, or shaping of thecatalyst/catalyst precursor, or formed upon the breakage or handling ofthe catalyst/catalyst precursor in the form of pieces or particles,e.g., fines, powder, and the like. In the process of making catalystprecursors, e.g., by spray drying, pelleting, pilling, granulating,beading, tablet pressing, bricketting, using compression method viaextrusion or other means known in the art or by the agglomeration of wetmixtures, forming shaped catalyst precursors, rework material isgenerated. Rework materials can also be generated from commerciallyavailable catalyst products, including supported and self-supportedcatalyst from such as ICR™ supported catalyst from Advanced RefiningTechnologies LLC, Nebula™ bulk catalyst from Albermale, or CRI™ NiMoalumina supported catalyst from Criterion Catalyst & Technologies,reduced to a size of less than 300 μm. In one embodiment, reworkmaterial consists essentially of unsulfided catalysts, made with orwithout the use of diluents or binders such as alumina, silica alumina,cellulose and the like.

In one embodiment, the rework material is prepared in a method asdescribed in US Patent Application No. 20110306490, incorporated hereinby reference in its entirety. The support material, e.g., alumina, ironoxide, silica, magnesia, titania, zeolite, etc., is first ground toparticles of less than 300 μm. Catalytic materials, e.g., double metalprecursors or single metal precursors such as ammonium heptamolybdate,or any soluble form of molybdenum, etc. are then deposited (impregnated)onto the ground base. The impregnated base is dried, then ground to aparticle size of 1 to 300 μm. In one embodiment, the deposition ofcatalytic materials is followed by calcination so the catalyticmaterials sinter with the metal in the support to effect loading. Thedeposition of catalytic materials can be carried out more than once tomaximize the catalyst loading, or different metal precursors can bedeposited onto the ground support base at the same time or as differentlayers for multi-metallic catalyst fines.

In one embodiment, the rework material for use as metal precursor feedhas an average particle size of less than 250 μm and greater than 1 μm.In a second embodiment, the average particle size is less than 75 μm. Ina third embodiment, an average particle size in the range of 2 to 50 μm.In a fourth embodiment, an average particle size of less than 20 μm. Ina fifth embodiment, less than 10 μm. The rework material can be groundor crushed to the desired particle size using techniques known in theart, e.g., via wet grinding or dry grinding, and using equipment knownin the art including but not limited to hammer mill, roller mill, ballmill, jet mill, attrition mill, grinding mill, media agitation mill,etc.

Sulfiding Agent Component: In one embodiment, a sulfided slurry catalystis formed with the addition of at least a sulfiding agent to inorganicmetal precursors. In one embodiment, the sulfiding agent is elementalsulfur by itself. In another embodiment, the sulfiding agent is asulfur-containing compound which under prevailing conditions, isdecomposable into hydrogen sulphide H₂S. In yet a third embodiment, thesulfiding agent is H₂S by itself or in a hydrocarbon mixture. In anotherembodiment, a sulfided slurry catalyst is formed in-situ by mixing themetal precursor feed with a heavy oil feedstock which releases asulfiding agent under sufficient conditions, generating a sulfidedslurry catalyst in-situ.

In one embodiment, the sulfiding agent is present in an amount in excessof the stoichiometric amount required to form the slurry catalyst. Inanother embodiment and depending on the metal precursor component (e.g.,metal precursor is a sulfur-containing organic compound), the totalamount of sulfur-containing compound is generally selected to correspondto any of about 50-300%, 70-200%, and 80-150%, of the stoichiometricsulfur quantity necessary to convert the Primary metal and the Promotermetals, if any, into for example, CO₉S₈, MoS₂, WS₂, Ni₃S₂, etc. In yetanother embodiment, the amount of sulfiding agent represents a sulfur tothe Primary metal mole ratio of at least 1.5 to 1 to produce a sulfidedcatalyst from the metal precursor(s). In another embodiment, the molarratio of S to the Primary metal is at least 3 to 1.

In one embodiment, the sulfiding agent is an aqueous solution ofammonium sulfide. The solution can be synthesized from hydrogen sulfideand ammonia—common refinery off-gases. In another embodiment, sour waterafter treatment is employed as the sulfiding source. Sour water iscommonly and cheaply available as wastewater from refineries, which maycontain anywhere between 1 to 50 wt. % ammonium bisulfide. In yetanother embodiment, recycled H₂S from process streams can also be usedfor the sulfiding process. Recycled H₂S stream is firstconcentrated/treated in gas removal units, using amine treating gasesknown in the art including but not limited to monoethanolamine (MEA),diethanolamine (DEA), methyldiethanolamine (MDEA), Diisopropylamine(DIPA), and mixtures thereof. In another embodiment, recycled H₂S istreated/recovered in a SELEXOL™ process. Synthesized ammonium sulfideand/or sour water can be stored in tanks prior to use. Since ammoniumsulfide solution is more dense than resid, it can be separated easily ina settler tank after reaction.

Hydrocarbon Transforming Medium (Diluent): In some embodiments within-situ sulfidation of metal precursors in a heavy oil feedstock, theslurry catalyst is transformed into an oil based slurry catalyst withthe in-situ sulfidation. In other embodiments with a water-basedcatalyst (with inorganic/water-soluble metal precursor starting feed), ahydrocarbon transforming medium (used interchangeably with “diluent” or“carrier”) is employed to transform a sulfided water-based catalyst(hydrophilic) to an oil based active catalyst (hydrophobic).

The nature of the hydrocarbon is not critical, and can generally includeany hydrocarbon compound, acyclic or cyclic, saturated or unsaturated,un-substituted or inertly substituted, and mixtures thereof, which isliquid at ordinary temperatures.

In one embodiment, the weight ratio of the water-based catalyst to thehydrocarbon diluent ranges from 1:50 to 10:1. In a second embodiment,the weight ratio of the water based catalyst to the hydrocarbon diluentranges from 1:10 to 5:1. In a third embodiment, from 1:5 to 1:1. In oneembodiment with a continuous transformation step, the ratio of catalystto hydrocarbon diluent ranges from 2:1 to 5:1. In another embodimentwith a batch transformation step, the ratio ranges from 1:1 to 2:1.

In one example, the hydrocarbon compound is derived from petroleum,including mixtures of petroleum hydrocarbons characterized as virginnaphthas, cracked naphthas, Fischer-Tropsch naphtha, light cat cycleoil, heavy cat cycle oil, and the like, typically those containing fromabout 5 to about 30 carbon atoms. In one embodiment, the hydrocarboncompound is a vacuum gas oil (VGO). In yet another embodiment, thediluent is a mixture of heavy oil and VGO. In another embodiment, thediluent is selected from the group of gasoline, distillate, naphtha,light cycle oil, benzene, toluene, xylene, etc. In one embodiment, thehydrocarbon compound has a kinetic viscosity ranging from 2 cSt to 15cSt @ 10° C. In a second embodiment, the hydrocarbon oil has a kinematicviscosity of at least 2 cSt at 10° C. In a third embodiment, from 5 cStto 8 cSt at 10° C. In one embodiment with the kinematic viscosity of thehydrocarbon transforming medium being below 2 cSt @ 10° C. or aboveabout 15 cSt @ 10° C., the transformation of the catalyst precursorresults in catalyst particles agglomerating or otherwise not mixing.

Optional Components: The slurry catalyst in one embodiment mayoptionally comprise other components including but not limited to poreforming agents, emulsifier agents, surfactants, sulfur additives,sulfiding agents, stabilizers, binder materials, phosphorus compounds,boron compounds, additional transition metals, rare earth metals ormixtures thereof, depending on the envisaged catalytic application.

Details regarding the description of metal precursor feed, optionalcomponents, other sulfiding agents, and other hydrocarbon transformingmedia are described in a number of patent applications and patents,including US Patent Publication No. 2010-0234212, U.S. Pat. Nos.7,754,645 and 7,410,928, the relevant disclosures are included herein byreference.

It should be noted that the optional components can be added in anyprocess step in the making of the slurry catalyst, depending on thenature of the optional components and the desired effect. In oneembodiment, binders are added directly to the metal precursors prior tothe sulfidation. In one embodiment with the use of emulsifiers, they areadded after the sulfidation of the metal precursors forming a sulfidedcatalyst. In another embodiment, the optional components are added tothe sulfidation step, e.g., sulfiding agents. In a third embodiment,optional components such as surfactants and the like are added to thetransformation step, or directly to the metal precursors or diluentsprior to the sulfidation of the metal precursors. In yet anotherembodiment, phosphorous-containing promoters, etc., can be addedseparately or in a mixture with the sulfiding agent and the metalprecursors to increase the incorporation of sulfur in the sulfidationstep.

Methods for Forming Slurry Catalysts: In one embodiment, the slurrycatalyst is prepared from at least a Primary metal component, e.g., aGroup VIB metal precursor and at least a Promoter metal precursor. Inanother embodiment, the catalyst is essentially free of Promoter metalwith no Promoter metal purposely added, e.g., prepared from Group VIBmetal precursor reagent(s). In another embodiment, the slurry catalystis prepared from at least Group VIII metal precursor reagent such asnickel sulfate as the sole starting feed.

The metal precursors can be added to the reaction mixture in solution,suspension or as such. If soluble salts are added as such, they willdissolve in the reaction mixture and subsequently be precipitated. Inone embodiment, the solution is heated optionally under vacuum to effectprecipitation and evaporation of the water.

In one embodiment, aqueous ammonia is brought into contact with at leasta Primary metal compound, such as molybdenum oxide or tungsten oxide,forming a water soluble oxygen-containing compound such as ammoniummolybdate or tungstate. In the next step, the Primary metal component insolution is brought into contact with at least a Promoter metalcomponent in solution, optionally with the adjustment of the pH to apre-selected pH by the addition of an acid, a base, or a suitablecompound which decomposes upon temperature increase into hydroxide ionsor H⁺ ions that respectively increase or decrease the pH, facilitatingthe formation of the double salt metal precursor. In one embodiment, thepH is controlled such that the pH at the beginning of the reactiondiffers from the final pH after precipitation. In another embodiment,the formation of the double salt metal precursor is via the reaction ofoil-soluble Primary metal compound and Promoter metal compound(s) in anorganic solvent under H₂-containing gas pressure, with the organicsolvent being a hydrocarbon mixture of alkanes and aromatic compounds.

The reaction of Primary metal and Promoter metal components to form thedouble salt precursor is carried out at a weight ratio of Promoter metalto Primary metal from 0.01:1 to 1:2 in one embodiment; from 0.05:1 to0.3:1 in another embodiment; 0.10:1 to 0.25:1 in yet another embodiment.In one embodiment, the Primary metal is a Group VIB metal and thePromoter metal is a Group VIII metal in a weight ratio of Promoter metalto Primary metal ranging from 1 to 49 wt. %. After the double salt metalprecursor is formed, the slurry mixture is optionally isolated from theliquid using methods known in the art such as filtration,centrifugation, decantation, or combinations thereof. After the doublesalt metal precursor is formed, it undergoes sulfidation and/ortransformation into an oil-based catalyst either in-situ upon contactwith a hydrocarbon feed, or in a separate sulfiding step and prior to atransformation step upon contact with a hydrocarbon diluent such as VGO.

Sulfidation of the metal precursor feed(s) can be done various ways. Inone embodiment, the Primary metal component is first sulfided prior toaddition of the Promoter metal precursor (unsulfided), generating apromoted sulfided catalyst precursor. In another embodiment, the Primarymetal precursor (unsulfided) is brought into contact with a sulfidedPromoter metal precursor and the mixture may or may not be sulfidedagain to form a catalyst precursor. In a third embodiment, the Primarymetal precursor is co-sulfided in the same step with the Promoter metalprecursor, and the sulfided catalyst precursor may or may not besulfided again for an enhanced sulfided catalyst precursor. In yetanother embodiment, the Primary metal precursor and the Promoter metalprecursor(s) are separately sulfided and combined, and the sulfided(combined) catalyst precursor may or may not be sulfided again for anenhanced sulfided catalyst precursor. In another embodiment without anyPromoter metals, the Primary metal precursor feed is sulfided beforetransformation with a hydrocarbon diluent. In yet another embodimentwith the use of double salt metal precursor(s) as feed, the double saltmetal precursor feed is sulfided generating a promoted sulfided catalystprecursor.

“Enhanced sulfiding” refers to the sulfidation of a metal precursor (ormixtures thereof) comprising at least one sulfided metal precursoragain, for an enhanced sulfidation scheme, resulting in a relativelyhigh ratio of S to Primary/Promoter metal(s) with improved catalyticperformance. In one embodiment of enhanced sulfiding (or “doublesulfiding” or two-step sulfiding), at least one of the Primary metalprecursor and the Promoter metal precursor is first sulfided at a sulfurto metal mole ratio of at least 1.5 to 1, then combined with the secondmetal precursor (un-sulfided or sulfided). The mixture is then sulfidedagain at a sulfur to metal mole ratio of at least 1.5 to 1, generating apromoted and enhanced sulfided catalyst precursor. The sulfiding agentcan be the same or different in the different sulfiding steps, and theamount of sulfiding agent (molar ratio of S to metal precursor) can bethe same or different in the first sulfiding steps.

In the various configurations as described above, the Primary metalprecursor feedstock and/or the Promoter metal precursor feed (if anypresent) can be fed into the system all at once, or any of the metalprecursor feedstock can be portioned and fed in stages. In oneembodiment with a Promoter metal precursor feed, the Promoter metalprecursor can be provided all at once, intermittently, or split intoportions and fed in stages. As used herein, a portion means at least 10%in one embodiment, at least 20% in a second embodiment, at least 40% ina third embodiment; and at least 60% in a third embodiment. In oneembodiment, the feed is split into two portions, with a ratio of firstto second staged feeding ranging from 1:10 to 10:1.

In one embodiment, a portion of the Primary metal precursor is firstsulfided prior to addition of a portion (or all of) the Promoter metalprecursor (unsulfided), generating a promoted sulfided catalystprecursor. A second charge of the Primary metal precursor is added tothe promoted sulfided catalyst precursor before or during thetransformation step. In one embodiment, the Promoter metal precursor isalso split, with a portion of the Promoter metal precursor feed for theco-sulfiding step with the Primary metal precursor, a second charge ofthe Promoter metal precursor feed is added after the sulfiding step, andanother charge of the Promoter metal precursor feed is made in thetransformation step with a hydrocarbon diluent. The promoter metalprecursor comprises at least a promoter metal salt selected from anacetate, carbonate, chloride, nitrate, sulfate, actylacetonate, citrate,and oxalate of a Group VIII metal, for promoter metal to primary metalratio from 1:30 to 5:1.

The split feed scheme in one embodiment reduces deposit build-up in theprocess of making the slurry catalyst. In one embodiment in theco-sulfiding embodiment, a portion (or all) of Primary metal precursorand a portion (or all) of the Promoter metal precursor(s) are combinedand co-sulfided together, with the remainder of the metal precursor feedbeing subsequently combined with the co-sulfided catalyst precursor, orto be charged in the transformation step to produce the final catalyst.

In one embodiment with enhanced sulfiding, a portion of the Primaryand/or Promoter metal precursor feed is added in the subsequentsulfidation step. In another embodiment, a portion of the Primary and/orPromoter metal precursor feed is added to a sulfided catalyst precursoralong with a hydrocarbon diluent in the transformation step,transforming the water-based catalyst precursor to a slurry catalyst forheavy oil upgrade. In yet another embodiment, at least 30% of thePromoter metal precursors is combined with all the Primary metalprecursor to form a double salt metal precursor, with the remainder ofthe Promoter metal precursor(s) being added in subsequent stages, e.g.,in the sulfidation step and/or in the transformation step. In oneembodiment with a multi-metallic slurry catalyst with at least a Primarymetal and at least two Promoter metals, the Primary metal precursor iscombined with one of the Promoter metal precursors in a co-sulfidingstep. The second (remaining) Promoter metal precursor is then combinedwith the co-sulfided catalyst precursor in a subsequent (additional)sulfiding step, or mixed in with a hydrocarbon diluent in atransformation step.

In the sulfiding step, the sulfidation is carried out at a temperatureranging from room temperature to 760° F. and for a period of up to 24hours, forming a sulfided catalyst precursor. In one embodiment, thesulfidation completes in 10 minutes or less. In one embodiment, thesulfidation is at 50-450° F. In yet another embodiment, the sulfidationis between 50-300° F. In another embodiment, the sulfidation is between60-150° F. In one embodiment, the sulfidation is at 0-3000 psig. In asecond embodiment, between 100-1000 psig. In a third embodiment, thesulfidation pressure is less than 500 psig. If the sulfidationtemperature is below the boiling point of the sulfiding agent, such as60-70° F. in the case of ammonium sulfide, the process is generallycarried out at atmospheric pressure. Above the boiling temperature ofthe sulfiding agent/optional components, the reaction is generallycarried out at an increased pressure, such as in an autoclave.

In one embodiment, the sulfidation step optionally includes blendingsulfiding additives, optional metal sulfide powders, and the like, intothe catalyst precursor mixture to further enhance the activity of thecatalyst. In one embodiment with the sulfiding step being carried outwith water-based metal precursor(s), the resultant product of thesulfiding step is a slurry in an aqueous solution. In one embodiment,analyses show that the catalyst precursor product of the sulfiding stepis catalytically active, although not in optimum form for use inhydroprocessing operations.

In one embodiment after sulfiding, the catalyst precursor is optionallyisolated from the liquid using methods known in the art such as drying,filtration, centrifugation, decantation, or combinations thereof, underan inert atmosphere comprising any of nitrogen, refinery gas, a gashaving little or no oxygen, and mixtures thereof. In another embodiment,the sulfided catalyst precursor is subject to reduction with a reducingagent at temperatures ranging from below ambient to above ambient.Examples of reducing agents include but are not limited to hydrogen,hydrogen sulfide, carbon monooxide, finely divided carbon, coke, sulfur,etc. In a reduction step, active metals are converted into a more activestate. For example, in one embodiment with Mo as a Primary metal, MoS₃with an oxidation state of 6+ may change its oxidation state to MoS₂with an oxidation state of 4+ and become a slurry. In the reductionstep, any metal precursor present also changes its oxidation state,e.g., Mo⁶⁺ and Mo⁵⁺ may change its oxidation state to Mo⁴⁺. The reducedform of active metals may or may not be chemically bonded with sulfur.The reduction step can be before or after the transformation step, or itcan occur con-currently in the transformation under reducing conditionsand with a reducing agent present (e.g., H₂).

In one embodiment after sulfiding, the catalyst precursor is subject toan ammonia removal step before the transformation step. In anotherembodiment, ammonia removal is concurrent with the transformation, asammonia is removed with the water in the transformation. In oneembodiment, the sulfided water based slurry from the sulfiding step issubject to a simple aqueous phase ammonia flashing step by cooling anddepressurizing the slurry stream Ammonia can be flashed off togetherwith any generated hydrogen sulfide and hydrogen present in the system.

In one embodiment, the sulfided catalyst precursor (as prepared fromwater-soluble metal precursor as feedstock) is mixed with a hydrocarboncompound (diluent) and transformed into an oil based catalyst wherein itis transformed from a hydrophilic to an oil based active catalyst(hydrophobic). In one embodiment of the transformation step, and in thepresence of a reducing agent such as H₂, reduction also takes place fora sulfided Primary metal such as molybdenum to change its oxidationstate. The transformation is at a temperature of 50-760° F. in oneembodiment; at a temperature of 100-500° F. in a second embodiment; at150-450° F. in a third embodiment. The pressure of the transformationstep is maintained in the range of 0-3000 psig in one embodiment;between 300-500 psig in a second embodiment. In a third embodiment, from1000-2500 psig. In a fourth embodiment, less than 2000 psig. In oneembodiment, the transformation residence time ranges from 30 minutes to3 hours. In another embodiment, from 1 to 2 hrs. In yet anotherembodiment, the residence time is less than 1 hour.

In one embodiment, the process conditions in thetransformation/reduction step are sufficient to form the final slurrycatalyst. In one embodiment, after the transformation step, the slurrycatalyst contains less than 5 wt. % water in one embodiment; less than 3wt. % water in another embodiment; between 0.01 to 2.5 wt. % water in athird embodiment; and between 0.025 to 2 wt. % water in a fourthembodiment.

In one embodiment with the use of a light oil such as naphtha (with aboiling point above the boiling point of water) as the hydrocarbontransforming medium, to keep the oil at liquid at a high temperature,e.g., a temperature above 392° F. (200° C.), the transformation step iscarried out at a pressure in the range of about 2,175 psig to about2,900 psig. With the use of naphtha, after the transformation step, thelight oil can be conveniently vaporized in order to obtain theconcentrated slurry catalyst.

In one embodiment, the transformation is under an inert atmospherecomprising any of nitrogen, refinery gas, a gas having little or nooxygen, and mixtures thereof. In another embodiment, the mixing is undera H₂-containing gas pressure. In another embodiment, hydrogen gas isadded before and after the reactor in which the hydrocarbon/catalystprecursor mixing takes place. In one embodiment, the H₂ flow to thetransformation step is kept at 100 to 2000 SCFB (“Standard Cubic Feetper Barrel” of hydrocarbon compound feed to the reactor). In a secondembodiment, the H₂ flow ranges from 300 to 1000 SCFB. In a thirdembodiment, the H₂ flow ranges from 200 to 500 SCFB.

In one embodiment, ammonia/water removal from the oil based slurrycatalyst can be carried out after the transformation step. The catalyststream in one embodiment is heated prior to depressurization andvaporization of ammonia/water. The resultant slurry mixture can godirectly to a hydroprocessing reactor without the need for ammonia/waterremoval, but the presence of water will take up unnecessary room in ahydroprocessing reactor. In one embodiment, the oil based slurrycatalyst mixture is passed to high pressure separator to remove waterfrom the slurry catalyst prior to entering a hydroprocessing reactor.Hydrogen may be added following reactor or directly into the highpressure separator to flash off water and residual H₂S in the slurrycatalyst.

In one embodiment, ex-situ sulfiding and/or the transformation step(s)can be eliminated by mixing a solution containing metal precursor(s)directly with a heavy oil feed stock, a hydrocarbon diluent (carrier),or a hydrocarbon diluent/heavy oil feedstock mixture at a high shearrate and under hydrogen pressure for a dispersion of at least a portionof the metal precursors in the hydrocarbon as an emulsion. In oneembodiment, the emulsion mixing step is carried out with the addition ofat least a sulfiding agent. In another embodiment, at least a sulfidingagent is added to the emulsion after the high shear mixing. The metalprecursor feed can be any of a PLS feed stream, a double salt metalprecursor in solution, a water-soluble metal precursor in solution, or amixture of water-soluble metal precursors in solution, e.g., a molybdatesolution, a zinc sulfate solution, a mixture of molybdate and nickelsulfate, etc. The emulsion in one embodiment is a hydrophobic,oil-dispersed catalyst precursor.

In one embodiment of the high shear mixing, the emulsion particles areformed as droplets and of micron sizes, e.g., from 0.1 to 300 μm in oneembodiment, at least 2 μm in a second embodiment, from 1 to 10 μm in athird embodiment, and between 0.5 and 50 μm in a fourth embodiment. Thestructure and droplet size of the emulsion can be optimized based onprocess performance requirement and operation cost. There are severalways to form the water-oil emulsion, using techniques and/or high shearequipment known to those of ordinary skill in the art, such as nozzles,in-line static mixers, impellers, turbolators, fluidizers, etc.Surfactants or other additives, e.g., emulsifiers, may be added to forma stable emulsion having the desired structure and droplet size. In oneembodiment, at least a portion (e.g., at least 30%) of the aqueousmetal/catalyst precursor is present as fine droplets dispersed in thehydrocarbon diluent (medium). In another embodiment, the hydrocarbondiluent is present as fine droplets dispersed in the aqueous catalystprecursor, which may subsequently go through emulsion inversion formingfine dispersion of the aqueous catalyst precursor in hydrocarbondiluent/heavy oil.

In one embodiment, the emulsion of oil-dispersed catalyst precursor canbe provided directly to a reactor for heavy oil upgrade with in-situsulfiding upon mixing with a heavy oil feedstock forming a slurrycatalyst. With a heavy oil feedstock, as the feedstock has availablesulfur source for sulfidation and under reaction conditions for thedesulfurization/release of the sulfur source (e.g., H₂S), the emulsioncatalyst precursor can be sulfided in-situ. In one embodiment, thein-situ sulfidation occurs under hydroprocessing conditions, e.g., at atemperature ranging from 752° F. (400° C.) to 1112° F. (600° C.), and apressure ranging from 1435 psig (10 MPa) to 3610 psig (25 MPa).

In one embodiment, after at least a portion of the inorganic metalprecursor(s) is dispersed in a hydrocarbon medium forming an emulsion,the emulsified mixture is optionally sulfided with the use of asulfiding agent such as hydrogen sulfide or other sulfiding agents. Inone embodiment, the sulfiding agent is in gaseous or solid form, asaqueous sulfiding media can interfere with the emulsion droplet size. Inanother embodiment, additional sulfiding agents can be added at thebeginning of the high shear mixing process to get the sulfidation of theemulsion started. In another embodiment, the sulfiding agents can becontinuously or intermittently added to the high shear mixing process.In one embodiment, the sulfidation takes from 10 minutes to 1 day. Inanother embodiment, from 30 minutes to 4 hours. After the sulfidingstep, the temperature is raised to remove water/transform the emulsioninto a slurry catalyst.

In one embodiment prior to injection into a reactor for heavy oilupgrade, the emulsion (with or without the addition of a sulfidingagent) undergoes a reduction step in the presence of a reducing agent.In yet another embodiment, during or after the high shear mixing orsulfidation step(s), the temperature of the emulsion is raised to removewater. The water removal/transformation is under hydrogen pressure andat a temperature of 50-600° F. in one embodiment; at a temperature of100-500° F. in a second embodiment; at 150-450° F. in a thirdembodiment. The emulsion catalyst can be reduced and dewatered on acontinuous or batch basis at a pressure up to 3000 psig with theaddition of a hydrogen source at a rate of 0.10 to 2 ft³ H2 to 100 g ofPrimary metal in the emulsion catalyst to remove at least 20% of thewater. In one embodiment, high shear mixing is also employed during thetransformation step with the choice of appropriate internals in theequipment, e.g., the use of impellers.

In one embodiment with the formation of an oil-dispersible metalprecursor, an inorganic metal precursor such as ammonium heptamolybdate(AHM) is brought into contact with an organic solvent at a ratio of 15to 50 wt. % metal precursor. In one embodiment, the contact is at anelevated temperature of at least 140° F. (60° C.). In one embodimentwherein the organic solvent is a sulfur-containing compound, e.g., DMSO,the sulfiding step can be skipped. The mixture can be brought intocontact directly with a hydrocarbon diluent or a heavy oil feed stockunder the presence of hydrogen, and optionally with a sulfiding agent,for a final concentration of 200 ppm to 2 wt. % Mo (as a wt. % of heavyoil feedstock), wherein a sulfided active slurry catalyst is generatedin-situ for use in heavy oil upgrade.

In another embodiment with the use of organometallic compounds as metalprecursors, e.g., an oil soluble organo-molybdenum complex such asmolybdenum naphthenate and molybdenum dithiocarbamate, thetransformation step can be omitted. The slurry catalyst can be prepareddirectly from the metal precursors by dispersing the oil solubleorganometallic compounds (with or without a Promoter) directly into theheavy oil feedstock, or a mixture of heavy oil feedstock and a diluentsuch as VGO. The mixture is allowed to soak under sufficient conditionsto in-situ thermally decompose the organometallic complex, and/or forthe heavy oil to release H₂S needed for sulfidation, converting themetal precursors into a finely dispersed sulfided catalyst in the heavyoil.

The sulfidation of the oil soluble organo-molybdenum complex can also becarried out ex-situ. In one embodiment, the sulfiding agent is elementalsulfur by itself. In another embodiment, the sulfiding agent is asulfur-containing compound which under prevailing conditions, isdecomposable into hydrogen sulphide. In yet a third embodiment, thesulfiding agent is H₂S by itself or in H₂. In another embodiment, theoil soluble organometallic compound(s) are dispersed in a hydrocarbondiluent such as VGO (instead of heavy oil feedstock), then allowed tosoak under sufficient condition for the metal precursors to thermallydecompose forming a finely dispersed sulfided catalyst. The sulfidedcatalyst can be subsequently mixed with heavy oil feedstock for upgrade.

In one embodiment, the metal precursor feedstock is optionally“pre-soaked” in the heavy oil feedstock for a sufficient amount of time,e.g., from 15 minutes to 4 hours, to enhance the catalyst dispersion aswell as the sulfidation, resulting in increased catalytic activity interms of the conversion rate as well as the resulting API of theoverhead product. In one embodiment, the pre-soaking is at a temperaturefrom 200 to 800° F. In a second embodiment, from 350 to 750° F. Thepre-soak tank in one embodiment is maintained at the same pressure asthat of the hydrocracking process for the upgrade of the heavy oilfeedstock.

In one embodiment with the use of high sulfur feeds, hydrogen sulfide inthe reaction zone resulting from the desulfurization of the feed can beused as a suitable sulfur source for the sulfidation forming an activesulfided catalyst in-situ. In another embodiment, additional sulfurcompounds (including elemental sulfur) can be used to assist with thein-situ catalyst sulfidation. In one embodiment, a sufficient amount ofelemental sulfur is added to the catalyst precursor (in the form of anemulsion) for molar ratio of elemental sulfur to Primary metal rangingfrom 3:1 to 100:1; and from 2:1 to 80:1 in another embodiment.

In one embodiment with the use of rework material, the rework materialcan be used by itself without additional metal precursor feedstock. Inanother embodiment, the rework material can be used as part of thecatalyst feed system and combined with a slurry catalyst formed by othermeans. In one embodiment, the rework material is combined with ahydrocarbon carrier (diluent), forming an unsulfided slurry catalystthat can be subsequently sulfided in-situ upon contact with a heavy oilfeedstock. In another embodiment, instead of using a hydrocarbondiluent, the rework is slurried in water as a carrier. In anotherembodiment, a sulfiding agent, e.g., H₂S, elemental sulfur, or ammoniumsulfide, is added to the rework materials in a hydrocarbon carrier undersulfiding conditions to form a slurry catalyst. In yet anotherembodiment, the rework material can be slurried directly in a heavy oilfeedstock, or a mixture of a heavy oil feedstock and a hydrocarbondiluent, for subsequent in-situ sulfidation forming a slurry catalyst.

In all embodiments, a sufficient amount of rework material is employedas a solid in an amount sufficient for the formation of a slurrycatalyst, and to provide a catalyst dosage of 20 to 5000 ppm Primarymetal (e.g., Mo) to heavy oil feedstock. In one embodiment, the amountof rework materials (in a powder form) ranges from 2 to 60 wt. % oftotal weight of the hydrocarbon diluent and/or heavy oil feedstock. In asecond embodiment, the amount ranges from 5 to 40 wt. %. In a thirdembodiment, a sufficient amount of rework material is used for a dosageranging from 20 to 1000 ppm of Primary metal to heavy oil feedstock. Inanother embodiment, a sufficient amount of rework material is used for adosage of 5 to 100 ppm Primary metal to heavy oil feedstock.

In one embodiment, the slurry (rework) catalyst can be used directly ina hydrocracking unit. In another embodiment, it is mixed with a heavyoil feedstock prior to heavy oil upgrade. In yet another embodiment, theslurry (rework) catalyst can be combined with a fresh catalyst, e.g., aslurry catalyst made from a metal precursor feed or PLS (not made fromrework materials) as catalyst feed to a hydrocracking unit for heavy oilupgrade. In one embodiment, the amount of slurry (rework) catalystranges from 5 to 100 wt. % of the total slurry catalyst needed for heavyoil upgrade. In a second embodiment, the amount of slurry (rework)catalyst ranges from 10 to 70 wt. %. In a third embodiment, from 15 to45 wt %. In a fourth embodiment, the slurry (rework) catalyst accountsfor less than 50 wt. % of the total amount of slurry catalyst. Theweight ratio may vary depending on a number of factors, including thetype of heavy oil feedstock to be processed, operating conditions of thesystem, availability of supplies (availability of rework materials),etc.

In one embodiment with a PLS stream as a feedstock, the PLS stream canbe mixed with at least another metal precursor feedstock, forming aprecursor mixture for a subsequent sulfiding step/transformation step.In another embodiment, the PLS is used as the sole feedstock. In oneembodiment, the PLS stream is combined with a sulfiding agent e.g., H₂S,elemental sulfur, or ammonium sulfide, etc., under sulfiding conditionsto generate a sulfided water-based catalyst precursor, then subsequentlytransformed to an oil-based catalyst upon mixing with a hydrocarbondiluent. In another embodiment, the PLS is combined with a hydrocarboncarrier under shear mixing conditions with a hydrogen source to generatean oil-dispersed emulsion. In one embodiment, a sulfiding agent such asH₂S, elemental sulfur, or ammonium sulfide, etc., is optionally providedat a molar ratio of sulfur to Primary metal in the range of 2:1 to 4:1to convert the oil-dispersed emulsion to a slurry catalyst. In yetanother embodiment, the PLS is mixed with a heavy oil feedstock or amixture of heavy oil and hydrocarbon carrier (diluent) such as VGO underhigh shear mixing to generate an oil-dispersed emulsion. The volumeratio of PLS to hydrocarbon diluent ranges from 1 to 50 vol. %,depending on the concentration of metal precursors in the PLS as well asthe hydrocarbon carrier employed. The emulsion catalyst (sulfided orunsulfided) formed with a PLS feedstock can be provided directly to ahydroprocessing system for heavy oil upgrade. In another embodiment, thetemperature of the emulsion catalyst is raised to remove water/transformthe emulsion into a hydrophobic, oil-dispersed slurry catalyst.

Optional Hydrogen Pretreatment: In one embodiment before the heavy oilupgrade, the slurry catalyst is optionally treated with hydrogen. In oneembodiment, the saturation/pre-soak with hydrogen improves the catalystactivity and reduces the formation of coke in the upgrade process. Thepre-treatment is expected to enrich the surface of the slurry catalystwith hydrogen and thus enable the reactions to happen quicker, and thusreduces coke formation. In another embodiment, the pre-treatmentenhances the catalyst area and porosimetry.

The optional hydrogen pre-treatment can be carried out in a pre-mixingvessel and/or in the transfer line. In one embodiment, a small amount ofwater can be injected into the pre-mixing vessel along with hydrogenduring the pre-treatment process. The pre-treatment (orpre-conditioning) temperature in one embodiment ranges from 200° F. to800° F. In a second embodiment, from 300° F. to 750° F. In a thirdembodiment, from 400° F. to 600° F. The pre-treatment time ranges from aminute to 20 hours in one embodiment; from 1 to 10 hours in anotherembodiment; and from 2 to 5 hours in a third embodiment. The hydrogenrate ranges from 500 to 15,000 scf per bbl of slurry catalyst inhydrocarbon diluent (standard cubic foot/barrel). In one embodiment, thepre-treatment pressure ranges from 1435 psig (10 MPa) to 3610 psig (25MPa). The hydrocarbon diluent in one embodiment contains at least 10 wt.% of a light oil such as VGO, cycle oil, gasoline, distillate, naphtha,light cycle oil, benzene, toluene, xylene, and mixture thereof.

It is believed that with hydrogen pre-treatment prior to beingintroduced into an upgrade system with a heavy oil feedstock, thecatalyst surface is enriched with hydrogen which improves catalyticactivity for faster reaction and reduced coke/sediment formation. Theslurry catalyst with hydrogen pre-treatment (or pre-conditioning) in oneembodiment provides an increase in reaction rate constant k-values interms of HDS (hydrodesulfurization), HDN (hydrodenitrification), andHDMCR (hydrodemicrocarbon resid) of at least 10% compared to a slurrycatalyst without the hydrogen pre-treatment step. In another embodiment,the increase in reaction rate constant is at least 15%. In oneembodiment, the slurry catalyst with hydrogen pre-treatment provides animprovement in porosimetry properties in terms of surface area, for anincrease in surface area and total pore volume (TPV) of at least 10%compared to a slurry catalyst without the hydrogen pre-treatment step.In another embodiment, the increase in surface area and TPV is at least15%.

It should be noted that any of the process steps can be operated in anyof continuous, batch mode, or combinations thereof. The steps can becarried out in any of batch, semi-batch, or continuously stirred tankreactors (CSTRs), and can be a vessel equipped heating means having amechanical stirrer, or a static mixer, or by means of a recirculatingpump. The components (feed streams) can be introduced simultaneously, orsequentially in any order to the reactor or vessel. The term “feedstream” refers to both continuous and batch processed. In oneembodiment, some of the process steps are carried out in a batch mode,and some of the process steps, e.g., the sulfidation step, are carriedout in the continuous mode.

In one embodiment, both the sulfiding and transformation steps arecarried out in continuous mode. In another embodiment, the sulfidationis in batch mode, while the transformation is in continuous mode.Continuous operation can eliminate the need of holding tanks for some ofthe feedstock, particularly some that requires careful handling.

The mixing of the components can be done within a continuous stirredtank, or it can be done by other means including an in-line static mixer(e.g., with a plurality of internal baffles or other elements), adynamic high-shear mixer (vessel with propeller for very high turbulent,high shear mixing), or any device capable of ensuring turbulent mixingknown in the art. It is desirable to obtain a high degree of dispersionof the metal precursors and/or the sulfided catalyst precursors in theheavy oil feedstock to achieve highly active catalyst. In embodimentswith the use of a high sulfur heavy oil feedstock, hydrogen sulfide isgenerated in-situ in the reaction zone, from feed desulfurization. Thegenerated H₂S can be used as a suitable sulfur source for thesulfidation of the metal precursors.

In one embodiment and depending on the type of equipment used, thecomponents are mixed under conditions sufficient for a flow with aReynolds number of at least 2000. In a second embodiment, the mixing issufficient for a Reynolds number of at least 3000. In a thirdembodiment, a Reynolds number ranging from 3200 to 7200.

Reference will be made to the figures with block diagrams schematicallyillustrating different embodiments of a process for making slurrycatalysts for heavy oil upgrade.

FIG. 1 illustrates the steps involved in one embodiment of the process.In reactor 10, at least a Primary metal precursor 11 such as ammoniumheptamolybdate is co-sulfided with at least a Promoter metal precursor13 such as nickel sulfate in aqueous solution, forming a sulfidedcatalyst precursor with the addition of the sulfiding agent 12.Optionally in one embodiment, additional Promoter metal precursor 13(same or different from the Promoter metal precursor added to theco-sulfiding step) is added after the co-sulfiding step. Theco-sulfiding can be in batch mode, continuous mode, or semi-batch mode.In one embodiment, the sulfidation is continuous to allow for smallerequipment and more stable operations.

In one embodiment, the reaction time in the mixing tank 10 ranges fromabout 1 hour to 10 hours. The temperature in one embodiment ismaintained at 30° C. to 100° C. at a pressure ranging from 100 to 3000psig. In one embodiment, the weight ratio of Promoter metal nickel (orcobalt) to a Primary metal precursor, e.g., a Group VIB precursor suchas a molybdenum compound ranges from about 1:100 to about 1:2. In oneembodiment, instead of feeding the Promoter metal precursor directly tothe co-sulfiding step 10, Promoter metal precursor 23 is added to thesulfided a Primary metal precursor after the sulfidation step 10.

The catalyst precursor from reactor 10 is moved to the nextreactor/mixing tank 20, wherein the catalyst precursor is transformedwith the addition of a carrier oil such as VGO 21 for a period of time 5minutes to 2 hours and at a temperature from room temperature to 70° C.Hydrogen 22 is continuously added to the mixture reaction zone, in oneembodiment ranging from 300 SCFB (“Standard Cubic Feet per Barrel,”meaning per barrel of hydrocarbon feed) to about 2000 SCFB. The pressureof the reaction zone generally ranges from about 0 psig to about 3000psig. Temperature of the reactor generally ranges from 150 to 300° C. Inone embodiment, the reactor 20 is a CSTR with high shear mixing tomaintain homogenous slurry in the reactor. Optional components (notshown) can be added to reactor 20 to increase the incorporation ofsulfur in the catalyst precursor formed in this step. The oil-basedslurry catalyst 24 is sent to storage tanks, or directly to ahydrocracking process. Vapor stream 24 comprising flashed-off water,methane, ammonia, H₂S, etc. is collected for subsequentrecycle/scrubbing.

FIG. 2 is a block diagram illustrating another embodiment to prepare thecatalyst composition with a double salt metal precursor as a startingfeed. In the reactor 10, at least an acid or base 24 is added to the atleast a Primary metal (e.g., Group VIB) metal precursor 11, e.g.,ammonium heptamolybdate solution, and the Promoter metal precursor 13,e.g., nickel sulfate in aqueous solution, to adjust the pH to apre-selected level to promote the formation of the double salt metalprecursor slurry 14. In one embodiment as shown, water is optionallyremoved from the metal precursor slurry 14 using methods known in theart, e.g., a filter 40, a decanter or the like, generating crystals orconcentrated slurry 41. Double salt metal precursor crystals 41 is mixedwith a hydrocarbon diluent or a heavy oil feedstock 41, e.g., in amixing tank, static mixer 41 or the like, under high shear mixinggenerating an emulsion catalyst that can be used directly for heavy oilupgrade, e.g., in a hydrocracker.

In FIG. 3, a pressure leach solution (PLS) or a leach slurry 17 is usedto provide the metal precursors needed to make the slurry catalyst.Although not shown, additional Group VIB metal precursor feed such asammonium heptamolybdate solution, nickel sulfate, and the like, can alsobe added in addition to the PLS in the sulfiding step. In one embodiment(not shown), the PLS feedstock can also be added directly to the heavyoil feedstock for in-situ sulfidation, generating a sulfided slurrycatalyst. Sulfiding agent 16 is added to mixing tank 30 (continuously orfor a batch mode operation). The sulfided catalyst precursor istransformed into an oil-based sulfided catalyst in the transformationstep 60 with the addition of a hydrocarbon transforming medium 51, whichcan be a heavy oil feed itself.

FIG. 4 illustrates another embodiment to make the slurry catalyst with aPLS. In this process, a pressure leach solution 17 from a metal recoveryprocess (e.g., recovering metals from a spent catalyst) containingvarious metal salts is used as the feed to mixing tank 30 with theaddition of a hydrocarbon carrier, or a heavy oil feedstock 51 underhigh shear mixing. Optionally, additional sulfiding agents 16 can alsobe added. In one embodiment (not shown), additional metal precursors canalso be added to this step, and with the emulsion catalyst beingsubsequently sent to heavy oil upgrade.

In FIG. 5, at least a Primary metal precursor 11 in solution, e.g., aninorganic molybdenum compound such as ammonium heptamolybdate solutionor a nickel compound, is sulfided with the addition of the sulfidingagent 16 in mixing tank 30. The sulfided water-based catalyst istransformed into an oil-based sulfided catalyst in the transformationstep with the addition of a hydrocarbon transforming medium 51, whichcan be a heavy oil feed itself. In the next step 51, the slurry catalystundergoes H₂ treatment with hydrogen saturation, prior to heavy oilupgrade.

In FIG. 6, at least a Group VIB metal precursor 11, e.g., an organicmolybdenum compound or an inorganic molybdenum compound such as ammoniumheptamolybdate solution is mixed directly with the Promoter metalprecursor 13, e.g., nickel sulfate in aqueous solution, and ahydrocarbon diluent or a heavy oil feedstock 51 in mixing tank 30, andoptionally with a sulfiding agent, wherein sulfidation of the metalprecursors takes place forming a sulfided slurry catalyst. In oneembodiment, the mixing is via the use of a high shear mixing equipmentand under hydrogen pressure forming an emulsion catalyst. In oneembodiment, the catalyst is further homogenized via in-line static mixer60.

FIG. 7 illustrates another embodiment to make slurry catalyst. In thisprocess, AHM solution 17 mix mixed with DMSO solvent 18 and optionally asulfiding agent 16 in mixing tank 30. A nickel salt promoter 13 is addedto the oil-dispersible metal precursor, and optionally with a sulfidingagent 16, wherein a sulfided slurry catalyst is formed. The slurrycatalyst is added to the heavy oil feed 51 forming an emulsion with theuse on in-line mixer 60, prior to the heavy oil upgrade step. In anotherembodiment (not shown), the nickel promoted catalyst precursor(unsulfided or unsulfided) undergoes a reducing step in the presence ofa reducing agent, e.g., H₂, wherein the sulfided Mo changes itsoxidation state.

FIG. 8 illustrates a variation of the embodiment in FIG. 7, with aseparate promotion step, and with the addition of a hydrocarbon diluentor a heavy oil feedstock mixture 81 to the oil dispersible emulsion instep 80 for to form an active slurry catalyst prior to the heavy oilupgrade step.

FIG. 9 illustrates yet another variation of the embodiment in FIG. 7,wherein a heavy oil feedstock/hydrocarbon transforming medium 51 isadded to directly to the emulsion mixture of inorganic metal precursor,e.g., AHM solution 11 and DMSO solvent 18, for the sulfidation/formationof a slurry catalyst prior to the heavy oil upgrade step.

In FIG. 10, at least a Group VIB metal precursor 11, e.g., an inorganicmolybdenum compound such as ammonium heptamolybdate solution is mixedwith a hydrocarbon diluent 19, e.g., VGO, under high shear mixing instep 30, forming a water-in-oil emulsion. Although not shown,temperature in sulfiding tank 70 is subsequently raised to transform thesulfided emulsion/slurry catalyst 32 to a hydrophobic, oil-dispersedslurry catalyst. The slurry catalyst is mixed with the heavy oilfeedstock 51 prior to the heavy oil upgrade step.

FIG. 11 illustrates another embodiment for making an emulsion catalystwith a pre-sulfiding step. In this process, at least a Group VIB metalprecursor 11, e.g., an inorganic molybdenum compound such as ammoniumheptamolybdate solution is mixed with a hydrocarbon diluent 19, e.g.,VGO, under high shear mixing in step 30, forming a water-in-oilemulsion. The mixture is optionally sulfided with the addition ofsulfiding agent (H₂S or elemental sulfur) 16. In one embodiment, theslurry catalyst is mixed with a hydrocarbon diluent or a heavy oilfeedstock 51 prior to the heavy oil upgrade step.

FIG. 12 illustrates another variation embodiment for making an emulsioncatalyst with no pre-sulfiding step. In this process, an emulsion ofinorganic metal precursor(s) 11 in a hydrocarbon diluent, e.g., VGO 19is formed. The emulsion mixture is mixed directly with a hydrocarbondiluent or a heavy oil feedstock/hydrocarbon diluent mixture 51 underappropriate conditions prior to the heavy oil upgrade step. Although notshown, temperature in tank 70 is subsequently raised to transform thesulfided emulsion/slurry catalyst 32 to a hydrophobic, oil-dispersedslurry catalyst. The slurry catalyst in one embodiment is mixed with theheavy oil feedstock 51 in prior to the heavy oil upgrade step.

FIG. 13 illustrates an embodiment to prepare a slurry catalyst usingrework material or ground residuum catalyst fines. In this process,ground catalyst material (rework) 11 is slurried in VGO diluent 18 togenerate a slurry catalyst precursor. Optionally in one embodiment, asulfiding agent 16 is added to the process to pre-sulfide the slurryprecursor. The mixture can be subsequently mixed with a heavy oilfeedstock 51 for upgrade in a hydrocracker unit.

FIG. 14 illustrates an embodiment to prepare a promoted slurry catalystfrom an oil soluble organometallic compound. Quantities oforganometallic metal precursor 11, nickel promoter 13, and a blend ofhydrocarbon diluent 18 are mixed together in mixing tank 30. The mixturewas subsequently allowed to thermally decompose in tank 70, generating asulfided slurry catalyst, which can be subsequently mixed with a heavyoil feedstock for upgrade. In one embodiment, additional sulfiding agentmay be optionally added to the tank 70.

In FIG. 15, the organometallic metal precursor 11 is mixed directly witha heavy oil feedstock 51 and optionally a Promoter precursor 13. Themixture is allowed to soak under hydroprocessing conditions for in-situsulfidation to take place, generating a sulfided slurry catalyst forsubsequent heavy oil upgrade.

FIG. 16 illustrates an embodiment with at least an additional sulfidingstep for a slurry catalyst with an enhanced amount of sulfur. In oneembodiment, a Primary metal source 11 such as Mo, e.g., an aqueousmolybdate solution (2 to 15% Mo concentration) is charged in the reactorvessel 30 and brought up to reaction conditions, e.g., temperatureranging from ambient to 300° F. and pressure up to 3000 psig. Asulfiding agent 16 is added for the first sulfidation step (at a molarratio of S/Primary metal of less than 4:1), generating an aqueous basedmolybdenum oxysulfide catalyst precursor. The sulfidation can be carriedout on a continuous basis or batch basis. In the same (or the next)step, the catalyst precursor is promoted with a second/different metal,e.g., a Group VIII metal as Promoter metal source 13, at a ratio ofPromoter to Primary metal of 1 to 49 wt. %. The promoted aqueous basedcatalyst precursor is subjected to an additional sulfiding step with theaddition of the same or different sulfiding agent feed 16. Theadditional sulfiding step can be in the same or different equipment(mixing tank 70), and at the same or different sulfiding feed ratio fromthe first sulfiding step (a molar ratio of S/Primary metal of less than4:1). The resulting sulfur enhanced water base catalyst is emulsifiedwith a hydrocarbon diluent 51 in step 80 at an oil to water basecatalyst wt. ration ranging from 1:10 to 10:1. The transformation stepcan be done on either batch or continuous basis, and it can be carriedout in the same equipment or different equipment from the sulfidingstep. In one embodiment, (not shown), the sulfided catalyst issubsequently reduced and dewatered (on a continuous or batch basis) at atemperature from ambient to 300° F. and pressure up to 3000 psig withthe addition of a hydrogen source at a rate of 0.10 to 2 ft³ H₂ to 100 gof Primary metal in the catalyst, generating sour water and an oil basedcatalyst. The slurry catalyst in one embodiment is mixed with the heavyoil feedstock 51 in prior to the heavy oil upgrade step 60.

FIG. 17 illustrates an embodiment to prepare a catalyst with Ti as apromoter. A primary metal source 11 such as Mo, e.g., an aqueousmolybdate solution (2 to 15% Mo concentration) is charged in the reactorvessel 30 and brought up to reaction conditions. A sulfiding agent 16 isadded for the sulfidation step. The catalyst precursor is promoted witha second different metal, e.g., a Group VIII metal as Promoter metalsource 13. The promoted aqueous based catalyst precursor is subjected toa transformation step with the addition of a hydrocarbon diluent 51 inmixing tank 70. A sufficient amount of a Ti metal source 85 such astitanium naphthenate solution is added to the transformed catalyst,generating a Ti—Ni—Mo slurry catalyst for use in heavy oil upgrade step60.

FIG. 18 illustrates an embodiment to prepare a single metal catalyst,e.g., with the use of nickel as the single metal. A Ni precursor 11 issulfided with a sulfur source such an ammonium sulfide solution. Thewater-based catalyst is transformed with a hydrocarbon diluent 51 inmixing tank 60, generating a nickel-based slurry catalyst for use inheavy oil upgrade step 80.

FIG. 19 illustrates an embodiment to prepare a Zn—Mo slurry catalyst. AMo source 11 such as Mo, e.g., an aqueous molybdate solution is chargedin the reactor vessel 30 along with a Zn source, e.g., a zinc sulfateheptahydrade, under high shear condition and hydrogen pressure andbrought up to reaction conditions. In one embodiment, the promotedcatalyst precursor is mixed directly with a hydrocarbon diluent or aheavy oil feedstock 51 in mixing tank 70. In another embodiment, asulfiding agent 16 is optionally added (dotted line), generating anaqueous based catalyst precursor which can be subsequently transformedwith the hydrocarbon diluent 51, forming an emulsion catalyst forsubsequent heavy oil upgrade.

FIG. 20 illustrates an embodiment for preparing a slurry catalyst withsplitting feeding of the Promoter metal precursor feed. In oneembodiment, a Primary metal source 11 such as Mo, e.g., an aqueousmolybdate solution is charged in the reactor vessel 30 and brought up toreaction conditions with the addition of a portion of Promoter metalsource 13, and a sulfiding agent 16 for a co-sulfiding step, generatingan aqueous based catalyst precursor. The sulfidation can be carried outon a continuous basis or batch basis. In the next step, additionalPromoter metal source 14 is optionally added for a post-promotion step,wherein the Promoter metal source 14 can be the same or different fromPromoter metal source 13 (or fed at the same or different rate). Thewater-based catalyst precursor is subsequently transformed into a slurrycatalyst with a hydrocarbon diluent 51.

In another embodiment, the Primary metal precursor 11 is first sulfided,then subsequently promoted with a Promoter metal source 14. AdditionallyPromoter metal precursor 15 (which can be the same or different fromPromoter metal source 14) is added along with a hydrocarbon diluent 51in the transformation step.

FIG. 21 illustrates an embodiment for preparing a slurry catalyst fromground/rework catalyst. A ground commercially available catalyst 11 ismixed with a sufficient amount of VGO for a slurried catalyst havingabout 250 ppm to 4.0 wt. % Mo in VGO. The slurried catalyst is mixedwith a heavy oil feedstock and optionally, a fresh slurry catalyst 24for use in hydrocracker for heavy oil upgrade.

It should be noted that any of the process steps in the Figures can becarried out in either a batch and/or continuous mode. In one embodiment,high shear mixing is desirable to prevent any of the metalprecursor/catalyst from settling or forming thick gel.

Characterization of the Slurry Catalyst: The slurry catalyst comprises adispersed suspension of particles in a hydrocarbon medium. Thehydrocarbon medium can be a heavy oil feedstock itself; a hydrocarbontransforming medium such as gasoline, diesel, vacuum gas oil (VGO),cycle oil (MCO or HCO), jet and fuel oils, and mixtures thereof; or amixture of heavy oil feedstock and a hydrocarbon transforming medium. Inanother embodiment, the hydrocarbon medium is the hydrocarbontransforming medium. In one embodiment with the use of at least a metalprecursor having a pH of at least 4, the slurry catalyst ischaracterized as having improved morphology and dispersioncharacteristics, particularly useful for the upgrade of heavy oilfeedstock.

In one embodiment, the slurry catalyst comprises a plurality ofsuspended or dispersed droplets in oil (“emulsion catalyst”) with thedroplets having a mean size of 0.1 to 300 μm. In a second embodiment,the dispersed particles or droplets have an average droplet size of 0.5to 150 μm. In a third embodiment, an average droplet size of 1 to 100μm. In a fourth embodiment, an average droplet size of 1 to 50 μm. In afifth embodiment, the droplet size is less than 20 μm.

In one embodiment, the slurry catalyst comprises a plurality ofdispersed particles in a hydrocarbon medium, wherein the dispersedparticles have an average particle size ranging from 1 to 300 μm. Inanother embodiment, the particles have an average particle size rangingfrom 2 to 150 μm. In yet another embodiment, an average particle size ofat least 5 μm. In a fourth embodiment, an average particle size of lessthan 50 μm.

In one embodiment, the slurry catalyst is characterized as having apolymodal pore distribution with at least a first mode having at leastabout 80% pore sizes in the range of 5 to 2,000 Angstroms in diameter, asecond mode having at least about 70% of pore sizes in the range of 5 to1,000 Angstroms in diameter, and a third mode having at least 20% ofpore sizes of at least 100 Angstroms in diameter. As used herein,polymodal includes bimodal and higher modal. In one embodiment, at least30% of pore sizes are >100 Angstroms in diameter. In another embodiment,at least 40%. In another embodiment, at least 70% of pore sizes are >100Angstroms in diameter. In one embodiment, at least 50% are in the rangeof 50 to 5000 Angstrom in diameter. In another embodiment, at least 75%of the pore volume ranging from 100 to 1000 Angstroms.

The slurry catalyst has a total pore volume (TPV) of at least 0.4 cc/g(per gram of catalyst in a solid form) in one embodiment; at least 0.6cc/g in a second embodiment; at least 0.8 cc/g in a third embodiment; atleast 1 cc/g in a fourth embodiment; and less than 3 cc/g in a fifthembodiment.

In one embodiment, the slurry catalyst is characterized as having arelatively high total surface area, as determined by the nitrogen BETmethod, of at least 100 m²/g. In one embodiment, the surface area is atleast 100 m²/g. In another embodiment, the surface area is in the rangeof 200 to 900 m²/g. In a fourth embodiment, the surface area is in therange of 50 to 800 m²/g. In a fifth embodiment, the surface area is inthe range of 100 to 300 m²/g. In a sixth embodiment, the slurry catalystis essentially free of Promoter metals and has a surface area is in therange of 300 to 800 m²/g. In a seventh embodiment, the slurry catalysthas a surface area of at least 300 m²/g.

In one embodiment, the slurry catalyst (as a multi-metallic or singlemetal catalyst) is of the formula(M^(t))_(a)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),wherein M is a Primary metal selected from Group VIB metals, non-nobleGroup VIII metals, Group IIB metals; L is optional as a Promoter metaland L is a metal that is different from M, L is at least one of a GroupVIII metal, a Group VIB metal, a Group IVB metal, and a Group IIB metal;b>=0; 0=<b/a=<5; 0.5(a+b)<=d<=5(a+b); 0<=e<=11(a+b); 0<=f<=18(a+b);0<=g<=5(a+b); 0<=h<=3(a+b); t, u, v, w, x, y, z, each representing totalcharge for each of: M, L, S, C, H, O and N, respectively; andta+ub+vd+we+xf+yg+zh=0. In one embodiment of a multimetallic slurrycatalyst (b>0), the Primary metal M is molybdenum and the Promotermetals are nickel and titanium. In an embodiment of a bi-metallic slurrycatalyst, M is molybdenum and L is zinc.

In one embodiment, the slurry catalyst is single metallic (b=0) withnickel as the Primary metal M. In yet another embodiment, the Primarymetal M of the single metallic slurry catalyst is molybdenum. The singlemetal catalyst formula can also be written as:(M^(t))_(a)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),wherein M is at least one of a non-noble Group VIII (IUPAC nomenclaturegroups 8-10) metal, a Group VIB metal (IUPAC nomenclature group 6), aGroup IVB metal (IUPAC nomenclature group 4), and a Group IIB metal(IUPAC nomenclature group 12); t, v, w, x, y, z, each representing totalcharge for each of the component (M, S, C, H, O, and N);ta+vd+we+xf+yg+zh=0; 0.5a<=d<=4a; 0<=e<=11a; 0<=f<=18a; 0<=g<=2a; and0<=h<=3a.

Use of the catalyst. The catalyst composition can be used in virtuallyall hydroprocessing processes to treat a plurality of heavy oilfeedstock under wide-ranging reaction conditions such as temperaturesfrom 752° F. to 1112° F., pressure from 1435 psig (10 MPa) to 3610 psig(25 MPa), and liquid hourly space velocities from 0.05 to 10 h⁻¹.

The hydroprocessing (or hydrocracking) can be practiced in one or morereaction zones and can be practiced in either countercurrent flow orco-current flow mode. By counter-current flow mode is meant a processwherein the feed stream flows counter-current to the flow ofhydrogen-containing treat gas. The hydroprocessing also includes slurryand ebullated bed hydroprocessing processes for the removal of sulfurand nitrogen compounds and the hydrogenation of aromatic moleculespresent in light fossil fuels such as petroleum mid-distillates, e.g.,hydroprocessing a heavy oil employing a circulating slurry catalyst.

The catalyst can be applied in any reactor type. In one embodiment, theslurry catalyst is applied to a fixed bed reactor. In anotherembodiment, the slurry catalyst is used as part of a catalyst feedsystem in an ebullating bed reactors, a slurry reactor, a recirculatingreactor, or a fluidized bed reactor used in the H-Oil process, theLC-Fining process, the H-Coal process, the heavy oil upgrade process aswell as others. In another embodiment, two or more reactors containingthe catalyst may be used in series with no catalyst recycle. In a thirdembodiment, the hydroprocessing reactors are used in parallel, also withno catalyst recycle. Details regarding operations of the hydroprocessingreactors in heavy oil upgrade, other sulfiding agents, and otherhydrocarbon transforming media can be found in U.S. patent applicationSer. Nos. 12/506,885; 12/506,840; 12/506,987; and 12/506,885, all with afiling date of Jul. 21, 2009; and U.S. patent application Ser. Nos.12/232,327; 12/233,439; 12/233,393; and 12-233,171, all with a filingdate of Sep. 18, 2008, the relevant disclosures are included herein byreference.

In one embodiment, the slurry catalyst is added to the feedstock(catalyst to oil ratio) at a rate of 0.01 to 3 wt. %. In a secondembodiment, at a rate of 0.25 to 2 wt. %. In a third embodiment, at arate of 100 to 20000 ppm active metals, e.g., Group VIB metals. In afourth embodiment, the catalyst is added to the feedstock at asufficient rate for the total amount of Mo in the reaction zone of 0.005to 0.5 wt. % (based on the total weight of the feedstock).

In one embodiment with the use of a slurry catalyst that has beensulfided more than once (e.g., double sulfiding) and with a catalystconcentration of at least 2000 ppm (wt. % Primary metal to heavy oilfeedstock), the catalyst load to the hydrocracking unit for heavy oilupgrade can be reduced at least 10% compared to a catalyst that is notsulfided more than once. In another embodiment, the catalytic load canbe reduced at least 20%.

In one embodiment, the slurry catalyst characterized as giving excellentconversion rates in the upgrades of heavy oil, i.e., giving a 1000° F.+conversion rate of at least 50% in the upgrade of a heavy oil having anAPI of at most 15, when applied at a rate of less than 1 wt. % activeGroup VIB metal (relative to heavy oil feedstock), a 1000° F.+conversion rate of at least 75% in a second embodiment, a 1000° F.+conversion rate of at least 80% in a third embodiment, and at least 90%in a fourth embodiment.

In one embodiment with the use of the slurry catalyst of the invention,at least 98.5% of heavy oil feed is converted to lighter products. In athird embodiment, the conversion rate is at least 99%. In a fourthembodiment, the conversion rate is at least 95%. In a fifth embodiment,the conversion rate is at least 80%. As used herein, conversion raterefers to the conversion of heavy oil feedstock to less than 1000° F.(538° C.) boiling point materials.

EXAMPLES

The following illustrative examples are intended to be non-limiting.Unless specified otherwise, the catalytic activity of the catalystsprepared in the examples are tested for hydrodenitrogenation (HDN),hydrodesulfurization (HDS), vanadium removal activity (HDV), andhydrodemicrocarbon residue (HDMCR). VR refers to “vacuum resid” or aparticular heavy oil feedstock.

VR#1 refers to a heavy oil feedstock having 29.9 wt. % Microresiduetester (MCRT), 25.7 wt. % hot heptane asphaltenes (HHA), 5.12 wt. %sulfur, 672 ppm vanadium, and API at 60° F. of 2.7.

VR#2 refers to a heavy oil feedstock having 21.8 wt. % MCRT, 11.01 wt. %HHA, 5.07 wt. % sulfur, 125 ppm vanadium, and API at 60° F. of 4.9.

% Mo/VR refers to the amount of molybdenum metal (in the catalyst) as apercent (in weight) of the heavy oil feedstock. In examples that cycleoil (a mixture of medium and heavy cycle oil, MCO or HCO) is added tothe heavy oil feedstock (in an amount of 40 wt. % cycle oil to heavy oilfeedstock), “VR” refers to the amount of the heavy oil feedstockexcluding the cycle oil.

Unless specified otherwise in the examples, the transformation ofwater-based catalyst is carried out in vacuum gas oil at a wt. ratio ofoil to water-based catalyst of 1.5 to 1.

Comparative Example 1

In this example, a slurry catalyst with a Ni:Mo ratio of about 10% wasmade. 33.12 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) wasdissolved in 100 g of water in a glass vessel fitted with an overheadmechanical stirrer, and 14.1 g of concentrated ammonia solution (28 wt.% NH₄OH in H₂O) was added. A solution of 8.1 g of nickel sulfatehexahydrate (NiSO₄.6H₂O) in 32 g of water was added to the firstsolution, all at ambient temperature, producing an emerald-greensuspension. This suspension was heated to 70° C. under atmosphericpressure, and 101 g of ammonium sulfide ((NH₄)₂S) solution in water(40-44 wt. %) was added slowly, over the course of 45 minutes. Afterthat, the mixture was heated with stirring for an additional 60 minutes.The volume of the reaction mixture was reduced in half on a rotaryevaporator. The resulting water-based catalyst precursor was transformedto a final oil-based catalyst with VGO and hydrogen in a pressure testautoclave.

Comparative Example 1A

The procedure is to make a slurry catalyst of a similar Ni:Mo ratio of10% as in Comparative Example 1. In this example, 9000 grams of ammoniumdimolybdate (ADM) solution (12% Mo) was heated to the followingconditions 750 RPM, 150° F. and 400 PSIG. To this heated ADM solution, agas stream comprising H₂S, 20% CH₄, 60% H₂ was bubbled through thesolution until the S/Mo atomic=3.4. After the H₂S addition, then anappropriate amount of nickel sulfate solution (8% Ni) was added to themixture for a Ni/Mo wt % of ˜10%. The product can be transformed to anoil base catalyst as in Comparative Example 1 on a batch basis, or acontinuous basis.

Comparative Example 2

The procedure is similar to Comparative Example 1, except with a higherNi:Mo ratio of ˜23%, using 33.12 g of ammonium heptamolybdatetetrahydrate to dissolve in 100 g of water mixed with 5 g ofconcentrated ammonia solution, in a glass vessel fitted with an overheadmechanical stirrer. A solution of 16.2 g of nickel sulfate hexahydratein 32 g water was added to the first solution, all at ambienttemperature, producing a green suspension. This suspension was heated to70° C. under atmospheric pressure, and 100 g of ammonium sulfidesolution (44 wt. %) was added slowly, over the course of 45 minutes.After that, the mixture was heated with stirring for an additional 60minutes. The rest of the procedures were as in Comparative Example 1.

Comparative Example 2A

The procedure is to make a slurry catalyst of a similarly high Ni:Moratio as in Comparative Example 2, wherein 9000 grams of ADM solution(12% Mo) was heated to the following conditions 750 RPM, 150 F and 400PSIG. To this heated solution, a gas stream comprising 20% v H2S, 20%CH4, 60% H2 was bubbled through the solution until the S/Mo atomic=3.4.After the H₂S addition, then an appropriate amount of nickel sulfatesolution (8% Ni) was added to the mixture for a Ni/Mo wt % of ˜23%. Theproduct can be transformed to an oil base catalyst as in ComparativeExample 1 on a batch basis, or a continuous basis.

Comparative Example 3

This Example is to make a Mo only slurry catalyst. 33.12 g of ammoniumheptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) was dissolved in 100 g ofwater in a glass vessel fitted with an overhead mechanical stirrer, and14.1 g of concentrated ammonia solution (28 wt. % NH₄OH in H₂O) wasadded. This mixture was heated to 70° C. under atmospheric pressure, and101 g of ammonium sulfide ((NH₄)₂S) solution in water (40-44 wt. %) wasadded slowly, over the course of 45 minutes. After that, the mixture washeated with stirring for an additional 60 minutes. The volume of thereaction mixture was reduced in half on a rotary evaporator. The rest ofthe procedures were as in Comparative Example 1.

Comparative Example 3A

The Example was to make a Mo only catalyst similar to ComparativeExample 3. In this example, 9000 grams of ammonium dimolybdate solution(12% Mo) was heated under the conditions of 750 RPM, 150° F. and 400PSIG. To this heated solution, a gas stream comprising 20 volume % H₂S,20% CH₄, 60% H₂ was bubbled through the solution until the S/Mo atomicis about 3.4. The product can be transformed to an oil base catalyst asin Comparative Example 1 on a batch basis, or a continuous basis.

Example 4

5.63 g of ammonium dimolybdate solution (12 wt. % Mo) was mixed with0.84 g of nickel sulfate solution (8 wt. % Ni), yielding a double saltmetal precursor in solution. A sufficient amount of the double saltprecursor was mixed with 112.5 g of heavy oil feedstock (VR#1 mixed withcycle oil at a wt. ratio of 60:40) for a concentration of 1 wt. % Mo (Mometal as a wt % of VR#1) in a 1 L batch hydrocracking unit. The cycleoil is a HCO:MCO blend at a ratio of 1:1. X-ray diffraction patternshows that the Mo—Ni double salt is composed of highly crystallizedhydrogen ammonium molybdenum nickel oxide hydrate H₆(NH₄)₄Mo₆NiO₂₄*4H₂O.

Example 5

Example 4 was repeated except that a sufficient amount of elementalsulfur was added to the in a 1 L batch hydrocracking unit containingheavy oil feedstock and double salt metal precursor mixture, for a molarratio of S to Mo of 3:1.

Example 6

Batch hydrocracking tests were carried out to compare the catalyst madein Comparative Example 1A with the catalysts of Examples 4-5. Sufficientamounts of the catalysts were added to separate batch units containing112.5 g of 60:40 VR#1 to MCO for a final concentration of 1 wt. % Mo.The three batch hydrocracking units were tested under hydroprocessingconditions of 805° F. temperature, 1600 psig hydrogen pressure, and for2 hours reaction time. Results are presented in Table 1, showing thatExample 4 with double salt metal precursor feedstock showed bettercatalytic performance and spent catalyst properties, suggesting thatnickel promotion has improved, and a low temperature sulfur source forsulfiding would improve vanadium removal.

TABLE 1 Catalyst % HDN % HDS % HDMCR Comp. Ex 1A 32.44 65.24 52.82Example 13 29.25 66.20 48.93 Example 14 41.05 74.58 52.14

Example 7

A sufficient amount of ammonium heptamolybdate (AHM) solution (12 wt. %Mo) was added to about 170 g of heavy oil feedstock in a 1 liter batchhydrocracking unit for 1 wt. % Mo to VR. The heavy oil feedstockcontaining a mixture of VR#1 as the vacuum resid (VR) and medium cycleoil at a weight ratio of 60:40.

Example 8

Example 7 was repeated, except that a sufficient amount of elementalsulfur was added to the unit for a S to Mo wt. % of 0.7:1.

Example 9

Example 8 was repeated, except that a sufficient amount of elementalsulfur was added to the unit for a S to Mo wt. % of 5:1.

Example 10

Example 9 was repeated, and the unit was heated up to 180° C. underhydrogen pressure of 1800-1900 psig for 2 hours.

Example 11

Example 8 was repeated, and the unit was heated to 180° C. underhydrogen pressure of 1800-1900 psig for 2 hours under mixing conditions.

Example 12

5.63 g of ammonium dimolybdate solution (12 wt. % Mo) was mixed with0.84 g of nickel sulfate solution (8 wt. % Ni) and about 170 g of heavyoil feedstock in a 1 liter batch hydrocracking unit (for 1 wt. % Mo toVR). The heavy oil feedstock containing a mixture of VR#1 as the vacuumresid (VR) and medium cycle oil at a weight ratio of 60:40. Elementalsulfur was added to the unit for a S to Mo wt. ratio of 5:1. The unitwas heated up to 180° C. under hydrogen pressure of 1800-1900 psig for 2hours under mixing conditions.

Example 13

Batch hydrocracking tests were carried out to compare the catalyst madein Comparative Example 1 with the in-situ sulfided catalysts made frommetal precursor feed in aqueous solutions of Examples 7-13. The startingconditions of the batch units included 1400 psig pressure at 160° F. Thebatch hydrocracking units were heated to 805° F. temperature and held atthat temperature for 2 hours reaction time, with sufficient catalyst fora concentration of 1 wt. % Mo in VR. Results are presented in Table 2,with analyses of the heavy oil in the batch reactors before and after.

TABLE 2 Mo:VR S:Mo API° N Wt. S MCR Example Wt. % wt. % 60 F./60 F. ppmwt. % wt. % Feed VR#1 n/a n/a 2.5 5500 2.99 18.46 Comp. Ex 1 1. n/a 12.4200 1.38 9.5 Example 16 1. 0 9.3 4900 1.90 12.74 Example 17 1. 0.7 10.64700 1.51 10.82 Example 18 1. 5. 11.9 4400 1.62 10.45 Example 19 1. 5.11.3 4300 1.52 9.98 Example 20 1. 5. 12.3 4200 1.39 9.87 Example 21 1.5. 12.6 4300 1.26 10.09 Comp. Ex 1 0.20 n/a 10.1 4600 1.74 12.07 Comp.Ex 1 0.04 n/a 9. 4000 1.93 13.37 Example 20 0.2 5. 10.7 4500 1.69 10.91Example 20 0.05 5 10. 3500 1.85 11.65 Blank - no 0 5 8.9 4350 2.38 14.96catalyst

Example 14

1.78 g of ammonium dimolybdate crystal was dissolved in 98.22 g of DIwater to prepare the molybdenum molybdate solution. A sufficient amountof ammonium hydroxide was added to the solution for the pH to be atleast 4. The solution was sulfided in an autoclave at 140° F. and 400psig with the injection of hydrogen sulfide to Mo at a molar ratio ofabout 3.4 to 1. The sulfided aqueous slurry was sent to a secondautoclave and mixed with VGO as a carrier oil for emulsification andtransformation purpose with supplemental H₂ at 400° F. and 400 psig sothat Mo sulfide compound formed could be reduced to Mo disulfidesuspended in VGO. After transformation, the water/carrier oil/solidslurry mixture was sent to the third autoclave at elevated temperature(470° F.) with supplemental H₂ so that water could be boiled off. Thepost-transformation slurry catalyst was delivered to a high pressureseparator, where the slurry oil based catalyst collected on the bottom,and water steam as well as other gases including H₂, H₂S, CH4, and NH3were removed for water, gas, and residual oil separation.

Example 15

35.82 g of nickel sulfate hexahydrate crystal was dissolved into 64.18 gof DI water for the nickel sulfate solution. A sufficient amount of theammonium dimolybdate solution as prepared in Example 14 was mixed withthe nickel sulfate solution for a wt % ratio of Ni/Mo=23%. A sufficientamount of ammonium hydroxide was added to the solution for the pH to beat least 4. The solution was sulfided in an autoclave at 14° F. and 400psig with the injection of hydrogen sulfide at a molar ratio of S/Mo ofabout 3.4 to 1. The sulfided aqueous slurry was sent to a secondautoclave and mixed with vacuum gas oil (VGO) as a carrier oil foremulsification and transformation at 400° F. and 400 psig, reducing Mosulfide compound Mo disulfide suspended in VGO. After transformation,the water/carrier oil/solid slurry mixture was sent to the thirdautoclave at elevated temperature (470° F.) with supplemental H₂ to boiloff water. The post-transformation slurry catalyst was delivered to ahigh pressure separator, where the slurry oil based catalyst collectedat the bottom, and water steam as well as other gases including H₂, H₂S,CH4, and NH₃ were removed for water, gas, and residual oil separation.

Example 15A

A sufficient amount of ammonium hydroxide was added to the ammoniumdimolybdate solution as prepared in Example 14 for the pH to be at least4. The solution was sulfided in an autoclave at 140° F. and 400 psigwith the injection of hydrogen sulfide at a molar ratio of S/Mo about3.4 to 1. After sulfidation of ammonium dimolybdate solution, asufficient amount of the nickel sulfate solution as prepared in Example4 was injected in and mixed with the post-sulfided aqueous slurry at awt % ratio of Ni/Mo=23%. The slurry was then transformed at 400° F. and400 psig with VGO, reducing Mo sulfide to Mo disulfide suspended in VGO.After transformation, the water/carrier oil/solid slurry mixture wassent to another autoclave at elevated temperature (470° F.) withsupplemental H₂ so that water could be boiled off. Thepost-transformation slurry catalyst was delivered to a high pressureseparator, where the slurry oil based catalyst collected on the bottom,and water along with H₂, H₂S, CH4, and NH₃ were removed for water, gas,and residual oil separation.

Example 16

BET characterization, pore porosity and pore size distribution werecarried out with slurry catalysts from Example 14 and ComparativeExamples 1A-3A. The wt. % of Mo in the post transformation slurrycatalyst of the Examples are shown in Table 3. The surface area valuesare 65 m²/g for Comparative Example 3A; 75 m²/g for Example 1A; 120 m²/gfor Example 2A; and 370 m²/g for Example 14. Total pore volume in cc/gfor Example 3A is 0.15; 0.22 for Example 1A; 0.33 for Example 2A, and0.86 for Example 14. Mesapore volume (PV of 25-1000 A) is 0.11 cc/g forExample 3A; 0.18 cc/g for Example 1A; 0.25 for Example 2A; and 0.68 forExample 14.

TABLE 3 Example % Mo Comparative Ex 3A 5.0 Comparative Ex 1A 4.8Comparative Ex 2A 4.8 Example 14 4.

Example 17

As the slurry catalyst of Example 14 shows significantly better surfacearea and porosity properties compared to the catalysts of the prior art,hydrocracking tests were conducted to evaluate the catalyst performance.In this example, different catalyst dosages were added to about 112.5 gof heavy oil feedstock to 1 liter batch hydrocracking units, heated upto a temperature of 805° F. and kept at a pressure of 1600 psig for 2hours. The heavy oil feedstock containing a mixture of VR#1 and mediumcycle oil at a weight ratio of 60:40. Results of the batch hydrocrackingtest are shown in Table 4.

TABLE 4 % Product % % % Catalyst Mo/VR API HDN HDS HDMCR Comp. Ex 3A1.00 9.2 32.4 65.2 52.8 Comp. Ex 1A 1.00 9.1 32.7 66.0 51.8 Comp. Ex 2A1.00 9.9 31.9 70.8 54.4 Example 14 1.00 11.7 39.5 76.4 60.6 Example 140.50 9.6 32.8 68.6 53.5 Example 14 0.25 9.1 35.1 67.5 51.7 Comp. Ex 10.25 6.9 23.0 59.5 43.2

Example 18

Heavy oil upgrade was carried out in a continuous unit operated with tworeactors in series, operating in once-through mode, i.e., with theeffluent stream from the first reactor comprising upgraded products, theslurry catalyst, hydrogen containing gas, and unconverted heavy oilfeedstock being sent to the second reactor for further heavy oilconversion. The reactor pressure varied between 2400 to 2500 psig. Thereactor temperature was kept at about 815 to 818° F. Hydrogen rate asscf per bbl VR was set at about 3000. LHSV was kept at about 0.125 hr⁻¹.The results of the Comparative Examples are shown in Table 5. The slurryin Example 14 performed much better than the comparative slurrycatalysts. For a catalyst concentration of 2909 ppm, the slurry catalystprovides surface area of 359 m²/g catalyst, available surface area of1741 m²/kgVR, TPV of 0.864 cc/g, mesapore volume of 0.864 cm³/g, andASPH of 6.1%. For a catalyst concentration of 1540 ppm, the slurrycatalyst provides ASPH of 8.9%.

TABLE 5 Catalyst Comp. Comp. Comp. Comp. Ex 3A Ex 3A Ex 2A Ex 2ACatalyst concentration, 4053 3064 3023 2739 C (ppm, gMo/gVR) CatalystProperties Ratio of active metals, 0 0 23 11 Ni/Mo (wt/wt) Surface areaof fresh 69 69 134 65 catalyst, SA (m²/g_(CAT)) Available surface area464 350 811 328 of fresh catalyst, C × SA (m²/kgVR) Pore volume of fresh0.142 0.142 0.332 0.232 catalyst, PV (cm³/g) Performance Asphaltenecontent 8.5 10.5 7.8 9.8 in heavy product, ASPH (wt. %)

Example 19

Example 18 was repeated except that VR#2 was used instead of VR#1,comparing the catalysts from Examples 14 and 15 with the slurry catalystfrom Comparative Example 2A. Results are shown in Table 6. With respectto porosimetry, Comparative 2A slurry catalyst provides a surface area(SA) of 157 m²/g, TPV of 0.358 cc/g; PV (<100 A) of 0.1324 cc/g; PV(>100 A) of 0.2256 cc/g; and PV (25-1000 A) of 0.264 cc/g. For theslurry catalyst of Example 14 at a concentration of Mo/VR of 1500 ppm,the results show a surface area of 373 m²/g; TPV of 0.864 cc/g, PV (<100A) of 0.4949 cc/g, PV (>100 A) of 0.3691 cc/g; and PV (25-1000 A) of0.683 cc/g. For the slurry catalyst of Example 15 at a concentration ofMo/VR of 1500 ppm, the results show a surface area of 221 m²/g; TPV of0.836 cc/g, PV (<100 A) of 0.1892 cc/g, PV (>100 A) of 0.6468 cc/g; andPV (25-1000 A) of 0.71 cc/g.

TABLE 6 Catalyst Comp. Ex 2A Ex. 14 Ex. 15 Mo/VR ratio, ppm 3000 15001500 Conversion Sulfur, % 80.93 74.86 81.17 Nitrogen, % 38.99 35.7038.47 MCR, % 72.95 72.33 75.68 VR (1000 F.+), % 88.34 89.70 88.81 HVGO(800 F.+), % 75.08 76.74 76.29 VGO (650 F.+), % 58.61 60.76 60.23 HDAs,% 66.43 67.61 76.38

Example 20

1.78 g of ammonium dimolybdate crystal was dissolved in 98.22 g of DIwater to prepare the molybdenum molybdate solution. A sufficient amountof ammonium hydroxide was added to the solution for the pH to be atleast 4. The solution was sulfided in an autoclave at 140° F. and 400psig with the injection of hydrogen sulfide at a molar ratio of S/Mo ofabout 3.4:1. The slurry was then transformed at 400° F. and 400 psigwith VGO, reducing water-based Mo sulfide to Mo disulfide suspended inVGO. After transformation, the water/carrier oil/solid slurry mixturewas sent to another autoclave at elevated temperature (470° F.) withsupplemental H₂ so that water could be boiled off. Thepost-transformation slurry catalyst was delivered to a high pressureseparator, where the slurry oil based catalyst collected on the bottom,and water along with H₂, H₂₅, CH4, and NH3 were removed for water, gas,and residual oil separation.

Example 21

BET characterization, pore porosity and pore size distribution werecarried out with slurry catalysts from Example 20 and ComparativeExamples 1A and 3A. Results of the Comparative Examples are presented inTable 7. Example 10 slurry catalyst provides a surface area of 319 m²/g,and a TPV of 0.55 cc/g.

TABLE 7 Wt. % Mo in Wt. % Mo in Surface Total pore water based oil basedArea Volume Example catalyst catalyst (m²/g) (cc/g) Comp. Ex 3 10.7 6565 0.15 Comp. Ex 1 9.4 75 75 0.22

Example 22

Heavy oil upgrade was carried out under conditions similar to Example 18with a continuous unit operated with two reactors in series. The resultsof the Comparative Examples are shown in Table 8. Example 20 with aconcentration of 3018 ppm Mo gives a surface area of 281 m²/g, and a PVof 0.862 cm³/g.

TABLE 8 Catalyst Comp. Comp. Comp. Ex 3A Ex 3A Ex 1A Catalystconcentration, 4053 3064 2739 C (ppm, gMo/gVR) Catalyst Surface area offresh 69 69 65 catalyst, SA (m²/gCAT) Pore volume of fresh 0.142 0.1420.232 catalyst, PV (cm³/g)

Example 23

A pressure leach solution was prepared according to the disclosure inU.S. Pat. No. 7,837,960 for the separation and recovery of base metalsfrom spent catalyst. The composition has a starting pH of about 3,containing 33 gpL free NH3, 80.9 gpL Mo, 7.9 gpL Ni, 0.17 gpL V, 277 gpLammonium sulfate (Amsul) and 10-gpL ammonium sulfamate.

Example 24

A sufficient amount of PLS solution from Example 23 was added to about170 g of heavy oil feedstock in a 1 liter batch hydrocracking unit for0.2 wt. % Mo to VR. The heavy oil feedstock containing a mixture of VR#1as the vacuum resid (VR) and medium cycle oil at a weight ratio of60:40. A sufficient amount of elemental sulfur was added to the unit fora S to Mo molar ratio of 75:1. The unit was heated up to 180° C. underhydrogen pressure of 1800-1900 psig for 2 hours.

Example 25

Example 24 was repeated, and the pre-soaked mixture was homogenized in ahigh shear mixer.

Example 26

Example 24 was repeated with the addition of 3 wt. % of sorbitanmonooleate (Span™ 80) as a wt. % of the PLS solution, before pre-soakand homogenizing in a static mixer for an emulsified mixture.

Example 27

Batch hydrocracking tests were carried out to compare the catalyst madein Comparative Example 1, with the in-situ sulfided catalysts made fromthe pressure leach solution of Examples 23-26. The starting conditionsof the batch units included 1400 psig pressure at 160° F. The batchhydrocracking units were heated to 805° F. temperature and held at thattemperature for 2 hours reaction time, with sufficient catalyst for aconcentration of Mo in VR as specified. Results are presented in Table9, with analyses of the heavy oil in the batch reactors before andafter.

TABLE 9 Mo:VR S:Mo API° N Wt. S MCR Example Wt. % wt. ratio 60 F./60 F.ppm wt. % wt. % Feed VR#1 - n/a n/a 8.9 4350 2.38 14.96 blank run Comp.Ex 1 0.2 n/a 10.1 4600 1.74 12.07 Comp. Ex 1 0.2 n/a 10.7 4500 1.6910.91 Example 23 0.2  0 9.8 4800 1.80 12.04 Example 24 0.2 25. 10.6 46001.84 11.12 Example 25 0.2 25. 11.3 4500 1.55 10.42 Example 26 0.2 25.11.8 4400 1.50 10.17 Comp. Ex 1 1.0 25. 9.5 4200 1.38 9.5

Example 28

Ammonium heptamolybdate was mixed with a hot (70° C.) DMSO to prepare asolution containing 11 wt. % Mo. The oil-soluble metal precursor wasmixed with a preheated feed. It is noted that DMSO forms H₂S on heatingwith H, therefore sulfur addition is optional.

Example 29

Example 28 was repeated with the addition of elemental sulfur to thefeed for a 0.7:1 S to Mo (wt. ratio).

Example 30

Batch hydrocracking tests were carried out to compare the catalysts madein Comparative Examples and the slurry catalysts made with theoil-soluble metal precursors formed from DMSO. A sufficient amount ofslurry catalyst was added to batch hydrocracking units for aconcentration of 1 wt. % Mo in VR (VR#1 used). The units were testedunder hydroprocessing conditions. Standard resid protocol tests wereperformed thereafter: initial 1400 psig H₂ (160° F.), then 90 min rampfollowed by 2 hr soak at 805° F. Results are presented in Table 10, withanalyses of the heavy oil in the batch reactors before and after. Thesulfur amount in the table (wt. %) indicates product characterization(indicative of HDS).

TABLE 10 Mo:VR API° N Wt. S MCR Example Wt. % 60 F./60 F. ppm wt. % wt.% Feed VR#1—blank run n/a 8.9 4350 2.99 14.96 Comp. Ex 3 1 11.3 46001.74 10.88 Comp. Ex 1 1 11.8 4400 1.42 10.58 Example 30 1 11.7 4600 1.5511.42 Example 29 1 11.2 4600 1.71 12.08

Example 31

A sufficient amount of Promoter metal precursor nickel sulphate wasadded to the sulfided oil-based catalyst precursor of ComparativeExample 3A for a slurry catalyst having a Ni to Mo weight ratio of 10%.

Example 32

A sufficient amount of Promoter metal precursor nickel naphthenate wasadded to the sulfided oil-based catalyst precursor of ComparativeExample 3A for a slurry catalyst having a Ni to Mo weight ratio of 10%.The mixture was heated to a temperature of 475° F. for 2 hours with theaddition of hydrogen.

Example 33

Example 32 is repeated, but nitrogen was used instead of hydrogen.

Example 34

A sample of Group VIB metal precursor molybdenum naphthenate 6% Mo wasprovided.

Example 35

A sample of Molyvan™ A, a molybdenum oxysulfide dithiocarbamate complex,was provided.

Example 36

A sufficient amount of Promoter metal precursor nickel naphthenate wasadded to a sample of Molyvan™ A in Example 35 for a catalyst precursorhaving a Ni to Mo weight ratio of 10%.

Example 37

The mixture of Example 36 was heated to a temperature of 475° F. for 2hours.

Example 38

A sample of OLOA-011007, a lubricant oil additive based on succinimidechemistry, commercially available from Chevron Oronite of San Ramon,Calif., was provided.

Example 39

To a 500 mL 3 neck round bottom flask, diethylene triamine (148.04 g,1.435 mol), and elemental sulfur (73.62 g, 2.296 mol) were charged. Thereaction mixture was allowed to stir and heat at 80° C. for 2.5 hrs.Ammonium dimolybdate (97.55 g, 0.287 mol) was then charged, and thereaction mixture was allowed to heat and stir for another 2 hours at120° C. 116 g of product was collected, and the rest was treated inExample 40.

Example 40

To the remaining reaction mixture from example 39, H₂O (300 mL) wascharged, and it was allowed to stir for 1 hour. The reaction mixture wasthen allowed to cool to room temperature. The precipitate was filtered,and washed with H₂O, ethanol, carbon disulfide, and diethyl ether.

Example 41

Batch hydrocracking tests were carried out to compare the catalysts madein Comparative Examples and the catalysts/precursors made in Examples31-39. A sufficient amount of precursors/catalysts from the Examples wasadded to batch hydrocracking units for a concentration of 1 wt. % Mo inVR. The units were tested under hydroprocessing conditions. Standardresid protocol tests were performed thereafter: initial 1400 psig H₂(160° F.), then 90 min ramp followed by 2 hr soak at 805° F. Results arepresented in Table 11, with analyses of the heavy oil in the batchreactors before and after.

TABLE 11 Examples HDN % HDS % HMCRT % 1000+ 800+ Comp. Ex 1A 44.2 81.266.7 87 71.7 Comp. Ex 3A 41.4 77.2 68 85.4 70.9 Example 31 48.7 77.1 —92.2 75 Example 32 44 79.3 65.9 83.5 67.3 Example 33 49.7 80.2 — 94.4 79Example 34 53.4 88.1 78 90.3 75.2 Example 35 61.6 88.5 78.6 90.8 74.1Example 36 74.1 95.5 87.9 94.2 83 Example 37 48.8 82.4 69.9 92.2 75.8Example 38 64.9 89.7 78.5 92.3 77.4 Example 39 45.4 75.5 — 83.5 71.9Example 40 44.1 74.4 — 86.2 72.8

Example 42

Rework was obtained by grinding a commercially available catalystprecursor (e.g., ICR 131 from ART Catalyst) to an average particle sizeof 40 microns or less (average particle size was 37 microns). The reworkwas mixed with a sufficient amount of VGO for a slurried rework having aMo and Ni content similar to the slurry catalyst of Comparative Example1 (about 1.5 wt. % Mo in VGO).

Example 43

Slurry catalyst from Comparative Example 1A was compared with theslurried rework metal precursor in Example 42. The materials were mixedwith a heavy oil feedstock VR#1.

Heavy oil upgrade was carried out in a continuous unit operated withthree reactors in series, operating in once-through mode, i.e., with theeffluent stream from the first reactor comprising upgraded products, theslurry catalyst, hydrogen containing gas, and unconverted heavy oilfeedstock being sent to the second and third reactors for further heavyoil conversion. The reactor pressure varied between 2475 to 2525 psig.The reactor temperature was kept at about 802-803° F. Hydrogen rate asscf per bbl VR per reactor was about 4500. LHSV was kept at about 0.09hr⁻¹. The results are shown in Table 12. With respect to porosimetry,Comparative Example 1A provides a surface value of 74.2 m²/g; a TPV of0.232 cc/g; and a PV (>100 A) of 0.1647 cc/g. Example 42 provides asurface value of 113 m²/g; a TPV of 0.382 cc/g; and a PV (>100 A) of0.2002 cc/g.

TABLE 12 Catalyst Comp. Ex 1A Ex. 42 Mo/VR ratio, ppm 4062 994Conversion Sulfur, % 92.44 95.42 Nitrogen, % 55.57 59.86 MCR, % 87.3489.56 VR (1000 F.+), % 93.28 94.52 HVGO (800 F.+), % 81.59 82.86 VGO(650 F.+), % 63.21 64.43

Example 44

33.12 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) isdissolved in 100 g of water in a glass vessel fitted with an overheadmechanical stirrer, and 14.1 g of concentrated ammonia solution (28 wt.% NH₄OH in H₂O) is added. A solution of 8.1 g of nickel sulfatehexahydrate (NiSO₄.6H₂O) in 32 g of water is added to the firstsolution, all at ambient temperature, forming a mixture having a Ni/Moratio of 10% (by weight). The mixture is heated to 70° C. underatmospheric pressure, and 101 g of ammonium sulfide ((NH₄)₂S) solutionin water (40-44 wt. %) was added slowly, over the course of 45 minutes.A sufficient amount of titanium napthanate solution is added to themixture for a Ti/Mo ratio of 10% (by weight) and stirred at 825° F.During heating, titanium naphthenate decomposes to produce a Ti/Ni/Mo/Scatalyst. The product can be transformed to an oil-base catalyst as inComparative Example 1A.

Example 45

A sufficient amount of titanium napthanate solution was added to thecatalyst from Comparative Example 1A for a Ti/Mo ratio of 10% (byweight) under the following reaction conditions: 725° F., 500 psig H₂and 3 hour soak, during heating titanium naphthenate decomposes toproduce a Ti/Ni/Mo/S catalyst, produced by ex-situ synthesis.

Example 46

Batch hydrocracking tests were carried out to compare the catalysts madein Comparative Example 1A and the catalyst made in Example 45. Asufficient amount of catalyst from the two Examples were added to VR#1in 1 liter autoclaves for a 1.25% Mo/VR wt. ratio. The autoclaves werepressurized to 1600 psig H₂, heat to 825° F. for 2.5 hours then allowedto soak at 825° F. for 5 hours. At the end of the soak, the reaction wasquenched, the liquid products recovered, and conversions werecalculated. Results are presented in Table 13, with analyses of theheavy oil in the batch reactors before and after.

TABLE 13 Test HDN % HDS % HDMCR % VR % (1000 F.+) Comparable Ex. 1A 54.387.8 79.0 96.2 Comparable Ex. 1A 50.2 85.5 79.2 97.1 Comparable Ex. 1A48.6 84.3 77.2 95.6 Ex. 45 57.7 89.9 82.1 95.6 Ex. 45 60.4 90.2 84.097.4 Ex. 45 57.7 90.6 82.5 96.4

Example 47

Appropriate quantity of nickel naphthenate oil soluble catalyst wasmixed with a heavy oil feedstock blend of VR#1 and cycle oil (HCO/MCO)at a 60:40 wt. ratio for a 0.75 wt. % Ni to feedstock, and charged intoa 1 liter autoclave. The autoclave was pressurized to 1600 Psig H₂,heated to 825° F. in 2.5 hours, and then allowed to soak at 825° F. for2 hours. A nickel sulfide slurry catalyst is generated from the thermaldecomposition products of nickel naphthenate and H₂S during the initialramp to 825° F. At the end of the soak, the reaction was immediatelyquenched, the liquid products were recovered, and conversions werecalculated from resulting liquid hydrocarbon product analyses.

Example 48

218 mL of water, 89.5 g of nickel sulfate hexahydrate, and 29.15 g ofconcentrated ammonium hydroxide solution in water (28 wt. % NH₃) werecombined in a glass flask fitted with an overhead stirrer and a nitrogenline to maintain inert atmosphere during reaction. The mixture wasstirred until complete dissolution. The resulting solution was sulfidedusing 60 g of 40 wt. % ammonium sulfide solution in water, at 70° C.under nitrogen blanket for 1 hour. The product was transferred intoanother flask, allowed to settle, and decanted to separate the solids.To a portion of these solids, containing ˜10 g of nickel, 200 g of VGOwas added, and the remaining water was evaporated in a reactor at204-232° C. (400-450° F.) in a flow of nitrogen under 400 psig pressure,yielding a black slurry product, containing the active catalystcomponent.

Example 49

Batch hydrocracking tests were carried out to compare the catalyst madein Comparative Example 1A (a standard Ni Mo catalyst) and the catalystmade in Example 47, which have compositions as shown in Table 14:

TABLE 14 Description Mo (%) Ni (%) S (%) C (%) H (%) N (%) Comparative9.45 0.88 9.67 68.19 9.33 1.03 Example 1 Example 47 0.00 8.62 8.82 61.8310.02 2.73

The slurry catalysts were mixed with a heavy oil feed (a blend ofVR#3/HCO and MCO) at a rate of 0.75% Ni to heavy oil feed for Example47, and 1.25% Mo to heavy oil feed for Comparative Example 1A, andcharged into 1 liter autoclaves. The autoclaves were pressurized to 1600Psig H₂, heated to 825° F. in 2.5 hours, and then allowed to soak at825° F. for 2 hours. At the end of the soak, the reaction wasimmediately quenched, the liquid products were recovered, andconversions were calculated from resulting liquid hydrocarbon productanalyses. It should be noted that nickel was charged on an equal molarbasis to the slurry catalyst in the Comparative Example. Table 15compares the hydrocracking results of the slurry catalysts of Examples47, 48, and Comparative Example 1A, showing comparable results under thesame reaction condition. It is further noted that Examples 47 and 48employ 60% less metals in the catalyst, and with less metal deposits(e.g., contaminants such as vanadium) the reactor, for a more effectivevanadium trapping effect.

TABLE 15 Wet % Conversion Solids Description HDN HDS HMCRT 1000+ 800+650+ (g) Comparative 45.8 82.5 70.1 93.2 77.7 57.9 3.7 Ex. 1A Example 4741.4 76.9 68.9 88.1 72.9 56.1 1.5 Example 48 42.0 74.7 64.1 92.9 78.358.4 4.5

Example 50

In this example, ex-situ slurry catalyst was prepared by thermaldecomposition of organometallic metal precursors (Molybdenumdithiocarbamate=Molyvan A −28% Mo and Nickel naphthenate −7% Ni in VGO).82 g of VGO, 35.7 g of Molyvan A, and 14.3 g of nickel naphthenate werecombined and homogenized. The mixture was added to 1 L autoclave andpressurized with 400 psig H₂, agitated at 300 RPM, and heated to 725° F.for an hour. The catalyst precursor thermally decomposed in-situ undersoaking condition of 725° F. for 3 hours. The reactor was cooled toabout 70° F. and depressurized. 300 g of toluene was added to thereactor and mixture was agitated for 15 minutes at 750 RPM. The slurrycatalyst was deoiled by centrifugation. 82 g of VGO was added to thedecanted slurry catalyst, and the slurry catalyst composition wasanalyzed. The ex-situ catalyst has an average particle size of 3microns, and shows an atomic S/Mo ratio of ˜2, suggesting an activecatalyst phase of MoS₂ promoted with nickel.

Example 51

In this example, in-situ promoted slurry catalyst is prepared.Appropriate quantities of Molyvan A and nickel naphthenate oil solublecatalyst precursors were mixed with a blend of VR#1/HCO/MCO (60:40ratio) to provide a wt. % of 1.25 Mo/VR (at 10% Ni/Mo wt.). The mixturewas charged into a 1 liter autoclave. The autoclave was then pressurizedto 1600 PSIG H₂, heated to 825° F. in 2.5 hours. Slurry catalyst wasgenerated from the thermal decomposition products of Molyvan A, nickelnaphthenate, and H₂S during the initial ramp to 825° F.

Example 52

In this example, in-situ slurry catalyst is prepared without anypromoter. Example 51 was repeated except without any nickel precursor,and slurry catalyst was generated from the thermal decompositionproducts of Molyvan A and H₂S during the initial ramp to 825° F.

Example 53

Batch hydrocracking tests were carried out to compare the catalysts madein Comparative Example 1A and the catalysts made in Examples 50-52.Catalysts from Comparative Example 1A and Example 50 were added to 1liter autoclave units for a concentration of 1.25 wt. % Mo in VR#1. Thecatalysts were tested under hydroprocessing conditions. The autoclaveswere then pressurized to 1600 psig hydrogen, heated to 825° F. in 2.5hours, and then allowed to soak at 825° F. for 2 hours. For thecatalysts of Examples 51-52, they were allowed to continue soaking inthe autoclave at 825° F. for 2 hours (after heating up to 825° F. in 2.5hours). At the end of the soak, the reaction was immediately quenched,the liquid products were recovered from the autoclave units, andconversions were calculated from resulting liquid hydrocarbon productanalyses. Results are presented in Table 16, with analyses of the heavyoil in the batch reactors before and after.

TABLE 16 Examples HDN % HDS % HDMCRT % 1000+ % Comparable Ex. 1A 46.682.75 70.53 93.34 Example 50 61.6 88.47 78.59 90.78 Example 51 74.195.45 87.87 94.20 Example 52 48.8 82.42 69.93 92.24

Example 54

The slurry catalyst from Comparative Example 3A was treated with a smallstream of H₂ (6800 SCF per BBL of catalyst feed) for about 3 hrs., andat 350° F.

Example 55

The pre-treated slurry catalyst from Example 54 was compared with theuntreated slurry catalyst from Comparative Example 3A. Withpreconditioning, the surface area of the slurry catalyst increased by17% from 69 to 81 m²/g, total pore volume increased by 23% from 0.142 to0.175 cc/g, and mesopore volume increased by 25% from 0.105 to 0.131cc/g.

Example 56

The slurry catalyst from Comparative Example 1A was treated with a smallstream of H₂ (6800 SCF per BBL of catalyst feed) for about 10 hrs., at atemperature of 350° F.

Example 57

The slurry catalyst from Comparative Example 1A was treated with a smallstream of H₂ (6800 SCF per BBL of catalyst feed) for about 10 hrs., andat a higher temperature of 600° F.

Example 58

Continuous heavy oil upgrade experiments were carried out to compare theslurry catalyst from Comparative Example 1A (not pre-treated) with thehydrogen treated catalysts from Examples 54, 56, and 57 (with hydrogentreatment). The continuous hydrocracking unit was operated in “recyclemode,” i.e., with at least a portion of the non-volatile fractionsrecovered from a flash separator in the unit was recycled back to one ofthe reactors in the unit. The unit was operated with an average reactortemperature of about 820° F. The reactor pressure varied between 2400 to2550 psig. The heavy oil feedstock was a VR#1: MCO mixture at a rate of60:40. Slurry catalyst was supplied to the unit at a rate equivalent toabout 4000 ppm Mo/VR. Each unit has 3 reactors in series, with aninterstage flash separator (IFS) located between the 2^(nd) and the3^(rd) reactor, and the 2^(nd) flash separator located after the last(3^(rd)) reactor. The non-volatile fractions from the first IFS aresupplied as feed to the second reactor, and a portion of thenon-volatile fractions from the 2^(nd) flash separator is recycled/sentback to the 1st reactor, with a small portion being removed as bleed(equivalent to about 8% of the heavy oil feedstock). The recycle streamis equivalent to about 20-30% of the total heavy oil feed to the firstreactor. Table 17 summarizes the results of the runs, showing 8-43%improvement in k-values due to the effect of the catalyst pre-treatmentwith hydrogen.

TABLE 17 Comparative Example Example Example 1A 56 57 Sulfur Conversion,% 95.58 94.09 95.12 Nitrogen Conversion, % 71.64 67.56 69.73 MCRConversion, % 97.17 95.73 96.69 VR (1000 F.+) Conversion, % 99.04 98.6698.83 HVGO(800 F.+) Conversion, % 93.88 92.73 93.75 VGO (650 F.+)Conversion, % 78.09 76.12 78.22 K Sulfur 5.79 4.94 5.52 K Nitrogen 1.651.44 1.55 K MCR 7.26 5.87 6.82 K VR 11.79 10.13 10.99 K HVGO 4.87 4.404.88 K VGO 2.09 1.93 2.12 API—slurry liquid filtrate 3.2 1.9 1.6API—high pressure overhead 36.0 35.4 35.5 stream API—Whole Product 33.6932.46 33.16

Example 59

9.04 g of stock 11 wt. % Mo ammonium heptamolybdate solution (equivalentto 1 g Mo) was mixed with 0.45 g of nickel sulfate hexahydrate(equivalent to 0.1 g Ni), and about 170 g of heavy oil feedstock in a 1liter batch hydrocracking unit (for a Mo:Ni ratio of 10:1 by weight anda catalyst concentration as Mo:VR of 1 wt. %). The heavy oil feedstockcontaining a mixture of VR#1 as the vacuum resid (VR) and cycle oil at aweight ratio of 60:40, for API° of 2.5 at 60° F., MCR in wt. % of 18.46and 5500 ppm of nitrogen. Elemental sulfur was added to the unit for a Sto Mo wt. ratio of 5:1. The unit was heated up to 180° C. under hydrogenpressure of 1800-1900 psig for 2 hours under mixing conditions topre-disperse the catalyst precursor in heavy oil.

Example 60

6.84 g of 15 wt. % Mo ammonium heptamolybdate solution (equivalent to 1g Mo) was mixed with 0.44 g of zinc sulfate heptahydrate (equivalent to0.1 g Zn) for a Mo:Zn ratio of 10:1 by weight, in a sufficient amount ofthe same heavy oil feedstock as in Example 62 for a catalystconcentration of 1 wt. % Mo:VR.

Example 61

Example 60 was repeated except with 6.84 g of 15 wt. % Mo ammoniumheptamolybdate solution (equivalent to 1 g Mo) and 2.2 g of zinc sulfateheptahydrate (equivalent to 0.5 g Zn), for a Mo:Zn ratio of 2:1 byweight, and the same catalyst concentration of 1 wt. % Mo:VR.

Example 62

Example 59 was repeated, except that the amount of heavy oil feedstockwas sufficient for a Mo:VR ratio of 0.2 wt. %, and a sufficient amountof elemental sulfur was added to the unit for a S to Mo wt. ratio of25:1.

Example 63

Example 60 was repeated, except that the amount of heavy oil feedstockwas sufficient for a Mo:VR ratio of 0.2 wt. % and a sufficient amount ofelemental sulfur was added to the unit for a S to Mo wt. ratio of 25:1.

Example 64

A number of batch hydrocracking tests were carried out to compare thecatalyst made in Comparative Example 1 with the in-situ sulfidedcatalysts made from metal precursor feed in aqueous solutions ofExamples 59-63. The starting conditions of the batch units included 1800psig pressure at 180° F. The batch hydrocracking units were heated to805° F. temperature and held at that temperature for 2 hours reactiontime. Results are presented in Table 18, with analyses of the heavy oilin the batch reactors before and after. Liquid yield means amount ofliquid obtained as a % of heavy oil feed.

TABLE 18 Mo:VR S:Mo API° N Wt. S MCR Example Wt. % wt. % 60 F./60 F. ppmwt. % wt. % Feed VR#1 n/a n/a 2.5 5500 2.99 18.46 Comp. Ex 1 1. n/a 12.4200 1.38 9.5 Example 59 1. 5.0 12.6 4300 1.26 10.09 Example 60 1. 5.012.4 4100 1.24 10.18 Example 61 1. 5.0 13.6 3900 1.26 9.15 Comp. Ex 10.2 n/a 10.1 4600 1.74 12.07 Example 62 0.2 25 11.4 4600 1.81 10.58Example 63 0.2 25 11.7 4600 1.40 10.69

Example 65

9000 grams of ADM solution (12% Mo) was heated to the 750 RPM at 150° F.and 400 PSIG. To this heated ADM solution, a gas stream comprising 20vol. % H₂S, 20% CH₄, 60% H₂ was bubbled through the solution for 4hours. After the H₂S addition, then an appropriate amount of nickelsulfate solution (8% Ni) was added to the mixture for a Ni/Mo wt % of˜23%. The mixture was then subjected to a second sulfiding step for 30minutes with the gas stream comprising 20 vol. % H₂S, 20% CH₄, and 60%H₂. The water based catalyst precursor was then drained from thereactor.

The water-based catalyst precursor slurry was transformed (continuousbasis) at 400° F. and 400 psig with VGO, resulting in an H₂S enhancedoil based catalyst. After transformation, the water/carrier oil/solidslurry mixture was sent to another autoclave at elevated temperature(470° F.) with supplemental H₂ so that water could be boiled off. Thepost-transformation slurry catalyst was delivered to a high pressureseparator, where the slurry oil based catalyst collected on the bottom,and water along with H₂, H₂S, CH4, and NH3 were removed for water, gas,and residual oil separation.

Example 66

A number of hydrocracking tests were carried out to compare the catalystmade in Comparative Example 2A (catalyst with 23% Ni/Mo level) with theH₂S enhanced oil based catalyst of Examples 65 at different levels of Moto VR#2 as shown. Table 19 summarizes the characteristics of theComparative catalyst after a continuous transformation step.

TABLE 19 % wt. Mo in Oil carrier: aqueous catalyst Wt. % Mo in Catalystcatalyst precursor oil-based Surface TPV type precursor wt/wt catalystarea m2/g cc/g Comp. 9.4 1.5:1 4.8 135 0.34 Ex. 2A Example 9.4 1.5:1 4.8112 0.34 65

In the Example, the reactors were operated in series for a continuoustest employing the catalysts in Table 19. Results of the runs arepresented in Table 20 including the reactor conditions. It is observedthat the catalyst with enhanced sulfur level (in a second sulfidingstep) provides better performance in heavy oil upgrade, in someembodiment, of at least 5% increase in desulfurization rate, among otherimprovements.

TABLE 20 Comp. Comp. Example Example Exam- Exam- Exam- 1A 1A ple 65 ple65 ple 65 LHSV (VR#2), h−1 0.12 — 0.11 0.11 — Ave H₂ rate, scf/ 1851 —1862 1857 — Bbl/reactor Mo/VR, ppm 2939 3000 3229 2393 3000 Ave. ReactorT 816.6 819 816.7 816.7 819 in ° F. K(VR) 1000° F.+ 5.8 5.12 6.0 6.15.32 K(HVO) 800° F.+ 3.2 2.67 3.3 3.3 2.72 K (MCR) 3.0 2.46 3.2 3.1 2.68K Sulfur 5.1 3.43 5.5 5.0 3.93 K Nitrogen 0.6 0.76 0.7 0.5 0.79

Example 67

33.12 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) isdissolved in 100 g of water in a glass vessel, and 14.1 g ofconcentrated ammonia solution (28 wt. % NH₄OH in H₂O) is added. Asolution of ˜8.1 g of nickel sulfate hexahydrate (NiSO₄6H₂O) in 32 g ofwater is added to the first solution, all at ambient temperature,forming a mixture having a Ni/Mo ratio of 5% (by weight). The mixture isheated to 70° C. under atmospheric pressure, and 101 g of ammoniumsulfide ((NH₄)₂S) solution in water (40-44 wt. %) is added slowly, overthe course of 45 minutes for a co-sulfided catalyst precursor having aNi/Mo ratio of 10% (by weight). The resulting water-based catalystprecursor is transformed to a final oil-based catalyst with VGO andhydrogen in a pressure test autoclave in situ

Example 68

33.12 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) isdissolved in 100 g of water in a glass vessel, and 14.1 g ofconcentrated ammonia solution (28 wt. % NH₄OH in H₂O) is added. Asolution of ˜4.051 g of nickel sulfate hexahydrate (NiSO₄.6H₂O) in 16 gof water is added to the first solution, all at ambient temperature. Themixture is heated to 70° C. under atmospheric pressure, and 101 g ofammonium sulfide ((NH₄)₂S) solution in water (40-44 wt. %) is addedslowly, over the course of 45 minutes forming a co-sulfided catalystprecursor with a Ni/Mo ratio of 5% (by weight). Another solution of˜4.051 g of nickel sulfate hexahydrate (NiSO₄.6H₂O) in 16 g of water ismix into the co-sulfided mixture for a final Ni/Mo ratio of 10% (byweight). The resulting water-based catalyst precursor with split Nimetal precursor feed is transformed to a final oil-based catalyst withVGO and hydrogen in a pressure test autoclave in situ.

Example 69

A number of hydrocracking tests are carried out to compare the catalystmade in Comparative Example 1A (catalyst with 10% Ni/Mo level) with theco-sulfided catalyst, and the catalyst made with a split Ni feed. Table21 summarizes the characteristics of the catalysts after atransformation step and table 22 summarizes the performance inhydrocracking test. The catalyst made with the split Ni feed has similarposimetry to the co-sulfided catalyst, but higher catalytic activitycompared to the co-sulfided catalyst. It was also noted that thecatalyst made with a split Ni feed had a reduced vanadium trapping inthe hydrocracking reactor by at least 5% compared to the ComparativeExample 1A, and surface area of 147 m²/g and 140 m²/g respectively forExamples 67 and 68 compared to 77 m²/g for Comparative Example 1A; a TPVof 0.411 cc/g and 0.400 cc/g respectively for Examples 67 and 68compared to 0.241 cc/g for Comparative Example 1A.

TABLE 21 Comparative Example Example Example 1A 67 68 Ni/Mo ratio (wt.%) 10 10 10 PV (<100 Å), cc/g 0.071 0.121 0.120 PV (>100 Å), cc/g 0.1700.290 0.280 PV (>200 Å), cc/g 0.123 0.238 0.220 % PV <100 Å 29.3 29.3 30% PV >100 Å 70.7 70.7 70

TABLE 22 Catalyst Comparative Example Example Example 1A 67 68 VR LHSV,h⁻¹ 0.09 0.09 0.09 Mo/VR, ppm 4200 4200 4200 Avg. Rx. Temp., ° F. 805.0805.0 805.4 Conversion: MCR 87.35 87.33 87.38 VR (1000° F.+) 94.00 94.2793.26 Rate constant (10⁻¹³ h) K Sulfur 6.00 5.24 6.27 K Nitrogen 1.351.26 1.40 K MCR 4.00 3.86 4.02 K VR (1000° F.+) 6.10 6.21 5.90

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. It isnoted that, as used in this specification and the appended claims, thesingular forms “a,” “an,” and “the,” include plural references unlessexpressly and unequivocally limited to one referent. As used herein, theterm “include” and its grammatical variants are intended to benon-limiting, such that recitation of items in a list is not to theexclusion of other like items that can be substituted or added to thelisted items.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to make and use the invention. The patentable scope is defined bythe claims, and may include other examples that occur to those skilledin the art. Such other examples are intended to be within the scope ofthe claims if they have structural elements that do not differ from theliteral language of the claims, or if they include equivalent structuralelements with insubstantial differences from the literal languages ofthe claims. All citations referred herein are expressly incorporatedherein by reference.

1. A slurry catalyst for use in hydroprocessing a heavy oil feedstock,wherein: the slurry catalyst comprises a plurality of dispersedparticles in a hydrocarbon medium, wherein the dispersed particles havean average particle size ranging from 1 to 300 μm, the slurry catalysthas a polymodal pore distribution with at least 80% of pore sizes in therange of 5 to 2,000 Angstroms in diameter, and the slurry catalyst isprepared from sulfiding and dispersing a metal precursor solution in ahydrocarbon diluent, the metal precursor solution comprising at least awater-soluble salt of a Primary metal selected from Group VIB, Group IIBmetals and Group VIII metals, the metal precursor solution having a pHof at least 4 and a concentration of less than 10 wt. % of the Primarymetal in solution.
 2. The slurry catalyst of claim 1, wherein thePrimary metal is molybdenum and wherein the water-soluble metal salt isselected from the group of molybdates, alkali metal heptamolybdates,alkali metal orthomolybdates, alkali metal isomolybdates,phosphomolybdic acid, molybdenum oxide, molybdenum carbide, molybdenumnitride, aluminum molybdate, molybdic acid, and mixtures thereof.
 3. Theslurry catalyst of claim 1, wherein the metal precursor solution furthercomprises at least a water-soluble salt of a Promoter metal selectedfrom any of Group IVB metals, Group VIII metals, and Group IIB metals,wherein the Promoter metal is different from the Primary metal, and thePromoter metal is present in a weight ratio of 1-50 wt. %. Promotermetal to Primary metal.
 4. The slurry catalyst of claim 1, wherein thePromoter metal is nickel and wherein the water-soluble metal salt of thePromoter metal is selected from the group of nickel acetate, nickelcarbonate, nickel chloride, nickel sulfate, nickel nitrate, nickelacetylacetone, nickel citrate, nickel oxalate, and mixtures thereof. 5.The slurry catalyst of claim 1, wherein at least 70% of the pore sizesare in the range of 5 to 1000 Angstroms in diameter.
 6. The slurrycatalyst of claim 1, wherein at least 50% of the pore sizes are in therange of 5 to 5000 Angstroms in diameter.
 7. The slurry catalyst ofclaim 1, wherein at least 30% of the pore sizes are at least 100Angstroms in diameter.
 8. The slurry catalyst of claim 1, wherein theslurry catalyst has a total pore volume of at least 0.5 cc/g.
 9. Theslurry catalyst of claim 6, wherein the slurry catalyst has a total porevolume of at least 0.8 cc/g.
 10. The slurry catalyst of claim 1, whereinthe catalyst has an average particle size ranging from 2 to 100 nm. 11.The slurry catalyst of claim 1, wherein the slurry catalyst has a BETsurface area ranging from 200 to 800 m²/g.
 12. The slurry catalyst ofclaim 1, the metal precursor solution having a pH of at least 4 and aconcentration of at least 0.1 wt. % of the Primary metal in solution.13. The slurry catalyst of claim 1, the metal precursor solution havinga pH of at least
 5. 14. The slurry catalyst of claim 1, wherein theslurry catalyst has a general formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),wherein M is a Primary metal selected from group VIB metals, Group VIIImetals, and Group IIB metals; L is optional as a Promoter metal and L isdifferent from M, L is at least one of a Group VIII metal, a Group VIBmetal, a Group IVB metal, and a Group IIB metal; b>=0; 0=<b/a=<5;0.5(a+b)<=d<=5(a+b); 0<=e<=11(a+b); 0<=f<=18(a+b); 0<=g<=5(a+b);0<=h<=3(a+b); t, u, v, w, x, y, z, each representing total charge foreach of: M, L, S, C, H, O and N, respectively; and ta+ub+v d+we+xf+yg+zh=0.
 15. The slurry catalyst of claim 14, wherein M is selected frommolybdenum, tungsten, and mixtures thereof and L is selected fromnickel, cobalt, and mixture thereof.
 16. The slurry catalyst of claim14, wherein the Group VIB metal is molybdenum and the slurry catalyst isessentially free of Promoter metals.
 17. The slurry catalyst of claim16, wherein b=0, and the Primary metal M is nickel.
 18. The slurrycatalyst of claim 1, wherein the slurry catalyst has a 1000° F.+conversion rate of at least 50% for the upgrade of a heavy oil feedstockhaving an API gravity of at most 15, when the slurry catalyst is appliedat a rate of less than 2 wt. % active Group VIB metal relative to thetotal weight of the heavy oil feedstock,
 19. The slurry catalystcomposition of claim 14, wherein the slurry catalyst has an X-ray powderdiffraction pattern with a first broad diffraction peak at Bragg angleof 8 to 18° and a second broad diffraction peak at Bragg angle of 32 to40° (from 0 to 70° 2θ scale).
 20. The slurry catalyst composition ofclaim 1, wherein the slurry catalyst comprises a plurality of dispersedparticles in a hydrocarbon medium selected from gasoline, diesel, vacuumgas oil, cycle oil, jet oil, fuel oil, heavy oil feedstock, and mixturesthereof.